Anal. Chem. 1984, 56, 174R-199R
Gas Chromatography Francis W. Karasek* Department of Chemistry, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1
Francis I. Onuska Canada Centre for Inland Waters, Burlington, Ontario, Canada L9R 4A6
Frank J. Yang Walnut Creek Division, Varian Instrument Group, Walnut Creek, California 94598
Ray E. Clement Ontario Ministry of the Environment, Pesticides Laboratory, Rexdale, Ontario, Canada L9R 4A6
This review covers the fundamental developments in the field of gas chromatography (GC) since the last review in this series appeared (1A) and covers developments in the years 1982-1983. Although the review does not attempt to exhaustively survey the literature, its contents are extensive. This only reflects the massive use of the GC technique as evidenced by estimates for 1983 of about $300 million in world-wide sales of GC instruments with projections for 1986 of $425 million (2A). These estimates include data systems, which increasingly have become an integral part of GC instrumentation. It is interesting to note that HPLC instrumentation, estimated at $365 million for 1983, now exceeds the total for GC. The trends seen in the previous review have continued to appear in this one. The high performance of wall-coated open tubular (WCOT) column chromatography and the ready availability of commercial fused-silica WCOT columns has led to their dominance in the field of complex mixture analysis and environmental trace analysis. Their use in GC-MS instrumentation has now become almost universal.
COLUMNS Column Theory and Techniques. Partial explanation of the anomaly in the relationship between the lo arithm of retention and the carbon number (log Rt(rel)= results from complex and simultaneous actions of several factors according to Buryan et al. (4B). The conditions for using the log Rt(rel)relation in identification of monohydric n-alkyl phenols were determined. Hydrogen-bond formation between the free phenolic OH group and the trixylenyl phosphate polar stationary phase or between the functional groups themselves is certainly not the most important factor. Buys et al. (5B)studied a system of series-coupled columns for the experimental investigation of nonthermodynamic contribution to the retention time in a system of 2 seriescoupled columns. The theory and experimental data agreed, and the importance of nonthermodynamic contributions to retention times was considered. Nonthermodynamic contributions to the retention time must be taken into account when the effect of individual column temperatures on the effective partition coefficient are considered. Conder et al. (7B)evaluated methods of measuring chromotographic retention on skewed peaks. Skewing is caused by a partition isotherm which is too strong for the sample size used. In this case, five different methods of estimating the infinite dilution retention from measurements on the eak have been described in literature. They were evaluated i o t h a priori and by experimental comparison with the true infiiite dilution retention for four gas-liquid partitioning systems free from adsorption effects. Peaks were studied for both directions of skew with skew ratios between about 0.2 and 5. Only the method of Littlewood, Phillips, and Price (J. Chem. SOC.
f(8$)
174 R
1955,1480)was satisfadory for both directions of skew though it is almost equalled in accuracy by one of the other methods for each direction of skew. Methods based on the peak maximum, even the most often used, are not recommended. These findings apply to typical circumstances where the columns contain a few hundred plates. Gelbin et al. (10B) presented an adsorption model in which damaged pores are distributed throughout a network of undamaged pores within a spherical particle. The model is intended to simulate highly skewed peaks. Pulse chromatographic measurements in fresh Na Mg A1 zeolites, using isobutane as a tracer, which only enters the macropores, yield response curves with a relatively low skew. They are readily fitted by a system of differential equations for diffusion in a monodispersive pore system. For hydrothermally treated zeolites, effective diffusivities and Henry constants were considerably lower and the skew higher than in fresh samples. Curve fitting with this model was satisfactory and the characteristic parameters are almost constant at the flow rates studied. Application of the model can be extended to adsorbents or catalysts with macroporous structures damaged by other forms of aging. Grec et al. (1IB) evaluated methods for determining the parameters in the van Deemter equation. A reliable method for their determination in the case of packed column was presented. Hou et al. (13B) presented the linear relations between the specific retention volume and the number of carbon atoms of stationary liquids, as well as the number of carbon atoms and boiling point of solutes on nonpolar, polar, and mixed stationary phases. The retention volume of alkanes with 5-10 carbon atoms and aromatic hydrocarbons with 6-9 carbon atoms were determined at 61.3-100.3 "C in hexadecane, heptadecane, and tetracosane stationary phases. Kaizuma (15B)showed that the retention time of nonsorbed solutes in gas chromatography differs from one sample to another in regions of low flow. In such cases, a simple hyperbolic relation exists betwen retention times and interdiffusion coefficients of such samples in the carrier gas. Since the relation can be expressed by a hyperbolic equation as a product of two nondimensional terms, the results obtained with different columns and carriers can be fitted to a line equation XY = 1. Absolute retention times can then be estimated. The results pertain to carrier flow only through interstitial space in the column and not through intraparticle pores. A new idea, called ideal retention volume, is proposed by Liu et al. (19B). It is defined as the retention volume of a compound on unit volume of the stationary phase which would just be the compound itself. It can be calculated by the formula Vided= d R T j M P , where d is the density of the stationary phase, P is the saturated pressure at temperature T(K), M is the molecular weight of the compound, and R is
QQQ3-27QQ/84/Q356-174R$Q6.5QlQ 0 1984
Amerlcan Chemical Society
GAS CHROMATOGRAPHY
Frmcb W. K n d la Fmlessmd cha*b by at the uniwsity d wat&no. on(ario. and a b hdds an a d w polsssorship In the chrnxstry Dspamnem 01 Arizona State Unhwsity He received hla B Sc w e e in F 1942 hm Elnhust Collags and hk Ph D w e e In 1952 horn O r e n State U n i v m C l y Hla research and teaching interests are In gas and liquid chromatography. GCIMSI m p u t e r s . and plasma chromatography Si1970 hk group has pioneered research on fundamental analytical meand deveIq)msm 01 tecmiqun tor bacd analysis 01 complex organic envC ronmemal mixhres He is a member ot me EdRorbl Board 01 A~llYfiCalLevers. C h e m p h e r e and lhe Intnmatmonal .Munsl of Envkonnmntal A n s M I a l Chemlsby
,a\9
Eng diploma horn Slovak Technical Univershy. Bratlsbva. his M.S degree horn Czech Technological University. Ragwt. and hh m D hom Pukyne university. Bmo F a the last 11 years he has headed a gas chro. matcgraphy and GCIMS laboratat me Anatyiial Mtmods CHYklon. Canada Csnhs lor Inland Waters. HIS research Interests BIB h envkonmental organk baw analylkal chsrnktry. including de"Bl0Pme"t 01 inrbumentation and memodobg with an emphasis on tmlc organic pollulants in water. d ment. tkh. and wiidiWe. Onuska cumentk serves on the AdViScw Board of
F
the universal gas constant. A plot of log V,, vs. 1/T gives a straight line. Lines for compounds in a homologous series intersect in a definite point which is just the same as the one obtained on an ordinary stationary phase. The method of ideal retention volumes can be applied to predict or check the position of intersection. Sometimes, if the density data a t different temperatures are not available, the Vidd can be adopted h t e a d of Vu in a plot to fmd the intersecting point, where Vidsll = 1.7 X 107/MP" and P" is in mmHg. The position of lntersection of some alkenes were predicted by this method and checked successfully by experiments. From the Vu of some alkenes on 16 different stationary phases givei in hterature and the retention volumes already known a t on, temperature, the retention volumes a t another temperature were calculated. The average error is about 5%.
The van Deemter equation was evaluated for determining the resolution or efficacy of chromatographic peaks in gas chromatography by Moody (208).An experiment for testing the equation was described. Novak et al. (21B)evaluated an equation for specific retention volumes of homologous compounds with temperature and methylene number. Generally, the specific retention volumes measured for four homologues a t different temperatures are sufficient for determining the contents of the equation. The accuracy of the Vu volumes calculated for a given methylene number and temperature data by the equation is proportional to the precision of replicate determinations of the Vu value of a given compound on a given instrument. Linear relations between the partial molar excess Gibbs function of a solute methylene group, AGE(CH , and the average McReynolds constant, N,and between AG (CHd and the individual McReynolds constants were determined for a set of 55 stationary phases. AU relations are identical for the given level of statistical si ificance. An analysis of the relations indicates that AGE(& and AI are equivalent criteria of polarity for stationary phases and that polarity can adequately he characterized by a single criterion (248). Suetaka et al. (258)studied the retention volume in GC theoretidy and experimentally. A linear relation was derived between the ratios of adjusted retention volume to column length (VR/Z) and the reciprocals of distribution coefficient (l/K') of solutes between mobile and stationary phases from theoretical considerations on the basis of the regular solution theory and the van Deemter equation. This relation was experimentally confirmed by GC for alkenes on squalane or Apiezon L a t 30 "C. This result suggests that the retention volume for any solute can be calculated from the equation if the formation of regular solution is expected between the solute and the stationary phase. Thumneum and Hawkes (27B) studied the relationship between the obstruction factor, y, and velocity. The dependence of the y on velocity was verified. T h e effects of diffusion coefficient and particle to column diameter ratio on the yvelocity relationship were investigated. The results are consistent with Hawkes' hypothesis that values of y a t low velocities are averages over tightly packed and loosely packed domains while a t high velocities they are weighted in favor of the loosely packed domains where there is more flow. Acree ( 1 8 ) derived an expression for the chromatographic behavior of alcohol solutes on binary solvent mixtures of inert hydrocarbons based on the KretschmerWiebe (1954) and Mecke-Kempter (1940) association models. The expression predicts a logarithmic relation between the partition coefficient of the solute and solvent components and is identical with an expression derived earlier for systems containing only nonspecific interactions. Alvarez et al. ( 2 8 ) reported liquid diffusivities of furan derivatives in dinonyl phthalate a t several temperatures. Measurements were made by GLC using glass beads coated with dinonyl phthalate. Mass transfer resistance in the gas and the liquid phase for the chromatographic separation were reported. Adsorption a t the gas-liquid interface was demonstrated by Aranciba (38)in hydrocarhon-ethylene glycol systems. Thermodynamic properties of solution and absorption a t the gas-liquid interface of these systems were determined. The contribution of Kelvin retention to the overall retention process was calculated and its significance for different systems was discussed. Evaluation of the enrichment factor in GC preconcentration of impurities was evaluated by Gavrilina (8B). On the basis of retention data obtained on a given adsorbent and a t a given trap efficiency a t different temperatures, new equations were proposed for the evaluation of the enrichment factor. They are suitable under various preconcentration conditions such as equilibrium saturation, complete trapping, and permissible losaes. The new equations can he used to select the optimum preconcentration conditions providing the necessary sensitivity. The methods for calculation of activity coefficients of volatile compounds at infinite dilution from retention times in GLC are reviewed with 53 references by Doleial et al. (98). Haken and Srisukh (128) examined molecular retention indices of alipathic esters (RCOOR') for use in structureretention relations for tentative identification. These relations with homologous esters, on the basis of retention plots and
4
ANALYTICAL CHEMISTRY. VOL. 56, NO. 5. APRIL 1984
-
175R
GAS CHROMATOGRAPHY
retention index increments, have shown that the slopes of plots representing homologous esters with the same number of carbon atoms in the acid chain (R) decrease as the value of R is increased. Similarly for the same number of carbon atoms in the alcohol chain (R’)the slopes decrease as the value of R’ increases with the phases considered. Retention of methyl esters follows boiling point. On stationary phases containing highly polarizable substituent groups, it was evident that a loss of linearity occurs with alcohol-ester plots. The effect of isomerization in the alcohol chain was most apparent with isopropyl esters and to lesser extents with isobutyl and isopentyl esters. It is apparent that the methylene group has a greater effect on retention when in the alcohol chain than in the acid chain. This effect has also been observed with a-alkyl acrylic esters. With unsaturated esters, the boiling point was of importance but the presence of a double bond in an alkyl group tended to reduce retention on a nonpolar phase, the decrease being accentuated where conjugation occurred. With increasing polarity of the stationary phase, retention of 2-alkanoates increased with respect to the carboxyl group. With increased phase polarity the retention of cis isomers of unsaturated esters was affected more than that of trans isomers. The study of surface acid-base and catalytic properties of solids by follow-up GC pulse techniques was performed by Jover et al. (14B).This technique can be employed to determine strongly irreversibly and strongly reversibly bound substrates on the surface of a solid. Some technical developments of the method, including the choice of the pulse size and the interval between successive pulses are described. Determination of surface acidity of Al(OH), samples used as seeds in the Bayer process as well as qualitative and quantitative characterization of the catalytically active fraction of several oxide surfaces indicate the wide range of applicability in surface analyses. The temperature dependence of the diffusion coefficients in the binary mixtures by the reversed-flow sampling technique was studied by Katsanos et al. (16B). An improved sampling procedure gives reversal-peaks twice the height of those obtained previously, increasing the sensitivity and precision of the method. The 43 diffusion coefficients determined for the six mixtures a t various temperatures show an average difference of 4.4% from those calculated from the Fuller-Schettler-Giddings relation. Determination of coefficients of mass transfer of acetone, ethanol, and C6H6on the Tenax sorbent and heats of adsorption, Henry coefficients, activation energy, and inner and surface mass transfer coefficients were determined by Karlin et al. (17B). Katsanos et al. (18B) determined mutual diffusion coefficients of two gases A and B in a empty GC column by letting component B enter at an intermediate position of the column and continuously flow through a part of it, as a carrier gas. Component A is injected in a small amount instantaneously at the end of the column with the detector placed at the other end. By repeatedly stopping and then restoring the flow of B after a short time, narrow extra peaks were produced, owing to the diffusion of A into B. An equation was derived giving the area under the curve of each stop-peak as a function of time of the corresponding stop. Data obtained show negligible variations with changes in the experimental parameters. O’Reilly (22B) demonstrated a conditioning procedure for chromatographic columns in which a benzene solution of HgClzis repeatedly injected onto columns of diethyleneglycol succinate; hitherto unparalleled column efficiency is obtained for the determination of methyl- and ethyl-mercury. After treatment, peak areas were reasonably constant but do tend to decrease up to 6% over a 5-h period. The beneficial effects were only temporary; however, the cycle of improvement and subsequent decline in column efficiency and sensitivity seem to be repeatable indefinitely. Pacholec et al. (238) suggested a homologous series of n-bromoalkanes to provide a retention index scale with electron-capture detection and a novel calibration method for use in GC-ECD. The accuracy and precision of this method was compared to the standard calibration curve method and internal standard method with bromobenzene as a test substance. The new calibration method is capable of a relative average error of 4-10% compared with an error of 12-20% with the 176R
ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
standard calibration curve method for concentrations above the detection limit. Multicolumn GC systems formed by several columns with different stationary phases and their application to the analysis of complex gas mixtures was reviewed by Castello (6B). Welton et al. (28B)described the concept of multidimensional gas chromatography. Examples of backflushing and heart cutting were examined by using the pressure balancing techniques. Benefits, such as a shorter analysis time, better separation, and easier quantitation of low level components that would otherwise be obscured by components of high concentration, were illustrated. Open tubular columns in series with packed columns were used. Tiley (26B) published results on nearly 200 ternary liquid systems obtained by GLC mixed-solvent experiments analyzed for conformitywith the Scatchard-Hildebrand-Flory-Huggins model of liquid mixtures. The expected quadratic relation between partition coefficients and volume fractions applied in most cases. Consistent values of solvent-solvent interaction parameters are not obtained when specific solute-solvent attractions exist. The use of alkane solutes apparently gives constant and meaningful values to these parameters even when specific solvent-solvent interaction occurs. A computer simulation of solute-additive complexing in a solvent medium shows a linear relation between partition coefficient and additive concentration at relatively low additive concentration but indicates that any calculation of formation constants by this method must involve considerable quantitative uncertaint y Winskowski (29B) employed a combination of a nonpolar SE-30with three different selective phases: WAX51, Siponate DS 10, and OV-225. Various chemical classes were identified from retention indices, such as aldehydes, esters, and alcohols. The reliability is increased by use of group-specific response factors of a photoionization detector and relating them to FID response factors. If aldehydes as well as ketones are present, these must be eliminated by conversion to the Schiff s bases. This will lead to peak vacancies compared to the chromatogram of an untreated sample. Deans-type column switching facilitates the interpretation of peaks and recognition of coincidence.
.
LIQUID PHASES Problems associated with classification of stationary phases according to polarity and selectivity using RohrschneiderMcReynolds classification and on the basis of thermodynamic characteristics were discussed (32C, 33C). A method was proposed for selecting a stationary phase for separation of complex mixtures of known composition. A compilation of solubility data for 240 solutes and 207 stationary phases was collected, and a method for calculatin solubility factors in GLC was refined (23C). It covers a w i b range of functional groups and structures. Predictability of retention indices on the basis of these solubility factors can be compared to the experimental data. Properties like octanol-water partition coefficients, air-water partition coefficients, and saturated vapor pressure at given temperature were predicted. An optimization method for selecting stationary phases based on subdividin the multidimensional space having the polarity factors an specific values coordinates was described by Vigdergauz and Bankoskaya (35C). The theoretical basis for using chemically reactive, complex-forming stationary phases and the results achieved in this area as reported in literature were reviewed (3C).Numerical taxonomy of the retention indices of the meth 1 and pentafluorobenzyl esters of chlorophenoxyalkyl aci& has been studied (7C). Taxonomy can be defiied as the classification of individual species into groups with respect to their mutual resemblance. In chromatography, two important similarity coefficients are the distance and the correlation coefficients. They were employed to determine the relations between stationary phases by constructing dendro rams. Classical chromatographic evaluation of thermo&namic characteristics on hydrogenated polypropylene oils was described by Singliar and Macho (29B). Petsev (24C) described an improved vapor-state coating method. Very good results regarding uniformity of the liquid layer are obtained by the fluidized-bed technique. The efficiency of the packings is better than the efficiency of packin s prepared by solvent coating. Ingraham et al. (13C) appliec! the concept of window diagrams to predict the op-
d
GAS CHROMATOGRAPHY
timum separation of mixtures of volatiles on properly optimized serially coupled columns composed of two precise lengths. Evaluation of a mixed-phase column packing for the determination of fumigant residues and barbituates was also reported (6C, 38C). Studies of liquid crystals as stationary phases has continued to receive considerable attention. Witkiewicz (37C) reviewed the properties and applications of liquid-crystallinestationary phases in GC. Columns with liquid-crystalline stationary phases were characterized and the temperature dependence of column retention properties were discussed. The relationship between the structure of liquid-crystalline phase and their separating properties was also considered. Use of liquid crystals as stationary phases in GC and thermodynamic studies of different solutes in two liquid crystals, based on azoxy-4,4'-(diundecyl a-methylcinnamate) and cholesteryl nonanoate, showed quasi-second-order transitions between mesophases. The kinetics of the transformations between cholesteric textures and isotropic phase were studied from the peak profiles on stationary phases modified by solute concentration effects (3C, 39C). Sakagami et al. (26C) used smectic stationary liquid-crystallinephases for the separation of positional isomers of dibromobenzenes, chloroacetophenones, chloronapthalenes, and methylbiphenyls. It was suggested that the unique selectivity of the smectic A and C states relative to the smectic B state can be explained by the difference in the molecular packing in the layer between the smectic B and the smectic A or C state. Oesterhelt et al. (22C) used three novel liquid-crystal phases on the basis of a 2-pyrimidinylbenzonitrilemoiety for separating of cis/trans isomers of 1,4-cyclohexanesand of Z/E-monounsaturated fatty acid methyl esters. The described nematic phases can be applied as GLC stationary phases at 60-180 OC. Polynuclear aromatic hydrocarbons in urban air were separated on N,N'-bis(p-phenylbenzy1idene)-a&-bi-p-toluidine which has a nematic liquid-crystalline property as reported by Valerio et al. (342). Fu et al. (12B) separated o-, m-, and p-nitrochlorobenzene by using ordinary aromatic liquid-crystal stationary phases and conventional Apiezon L, Versamide 930, OV-25, OV-210, XE-60, OV-225, Igepal CO-880, PEG-ZOM, DEGA, and EGS. The experimental results indicate that the liquid crystals are less suitable for stationary phases than the conventional phases. PEG-2OM was most effective. A mixture of the C6H4C1N02isomers were completely separated on a 150-cm column within 8 min. Watabe et al. (36C) investigated various aspects of adsorption phenomena in an electric field on columns coated with liquid crystals. It was shown that the adsorption is influenced not only by the dielectric constant but also by the structure of the carbon skeleton. The equation pro osed previously for the relation between the field strength a n f t h e extent of adsorption was modified by introducing a structural term f,. Subsequently, the dielectric constants of esters were calculated from the equation by using the f, values of the corresponding alcohols and were compared with those found in literature. The difference was 10%. High-performance separation of hydrocarbons on cholestric mesophase columns was described by Sojak et al. (30C,31C). The results were compared with separation obtained on common stationary phases. Structure retention correlations, retention indices, and homomorphy factors were discussed. The cholestric modification showed a higher selectivity for trans-cis isomeric n-alkenes than the nematic and smectic mesophases or the common stationary phases. An excellent novel mesogenic polysiloxane stationary phase was described and compared with poly(methylphenylsi1oxane)separation for isomers of polycyclic aromatic hydrocarbons. The stationary phase yielded high column efficiency and yet concomitant high selectivity for isomers of PAH and sulfur-containing heteroaromatic compounds. The nematic temperature range of the new phase, 70-300 O C , exceeds those of previously described liquid-crystal stationary phases as reported by Kong and Lee (18C).
Low molecular weight polyethylene as a stationary phase of a low polarity which can be used at temperatures up to 300 "C was developed by Singliar (28C) further investigation showed that its overall polarity is lower than that of squalane. The phase can separate m-xylene from p-xylene. Polyperflouroalkyl ether can be used as an efficient stationary phase generating up to 2500 theoretical plates/m. Maximum allowable operating temperature for polyperfluoroalkyl ether
is at 275 "C. This stationary phase can be used to separate nonpolar and moderately polar organic compounds as stated by Dhanesar and Poole (4C, 8C, 9C, 1OC). Evaluation of substituted polyphenyl ethers as polar stationary phases was studied (25C). Five- and six-ring meta-linked polyphenyl ethers containing -NO2, -Br, Ac, -CH,Cl, and CN substituents were prepared. The reaction conditions used gave isomeric mixtures which were analyzed by reversed-phase chromatography (14C). The cyano-substituted polyphenyl ethers had similar polarity to Carbowax 20M and Silar 5C and were more thermally stable. Cyanosilicones as stationary phases were synthesized by Markides et al. (19C). A procedure was presented for the preparation of fused-silica and soda-glass OTC columns. Efficiency and deactivation were obtained by silanization at high temperatures by means of &-(cyanopropy1)cyclotetrasiloxane. Use of crystal hydrates as stationary phases was evaluated by using Mg(N0 )2.6H20and AL(N0&.9H20 on Celite by Berezkin et al. (16). Doering et al. (11C) evaluated polyhydric alcohols as a stationary phase. Retentions of C1-C7 alcohols on Sorbitol go through a minimum with increasing number of carbon atoms as a result of the increasing importance of absorption over partition in the retention mechanism. This effect can be used in examining methanol purity, since all the impurities will elute before methanol.
SOLID SUPPORTS Sakodynskii (230) reviewed present-day sorbents employed in GC. Favorable properties of a new adsorbent prepared by acid-base treatment of volcanic scoria were investigated and compared with those of Chromosorb W. It is claimed that the volcanic origin solid support is superior in chromatographic qualities to commerciallyavailable supports (ID, 20). Similar claims are announced by Laperashvili et al. (150) about natural Armenian neomberian deposits pretreated with 6 N HC1. It exhibits good chromatographic support qualities for saturated and aromatic hydrocarbons and C1-C5 alcohols. The changes in geometric and crystallographicstructures of Polish diatomaceous supports and Chromosorb P, after washing with HCl gas at elevated temperatures, were examined by Suprynnowicz and Tracz (260). Felt1 et al. (80,90) studied a new type of active carbon. The adsorption of C2-C5 alkanes, C2-C alkenes, acetylene, C02, H2S, and SO2 were studied. The differential heats of adsorption were calculated by the linear-regression method from the temperature dependence of the specific retention volumes, and the usefulness of the micropacked column for determination of adsorption thermodynamic quantities was evaluated on the basis of the results obtained. Zhubanov et al. (300) patented the sorbent which consists of an inert porous inorganic support and 5-6% of a thermoplastic polymer coating. To increase the selectivity of the separation of aromatic oxygen- and nitrogen-containing compounds a polyamidoimide was used as the coating and diamines and imidocarboxylic acids were also used as the polymer coatings. Carbopack B was coated using Oronite NIW. In general, the Oronite NIW packing results in improved peak shape, enhanced separating power, and faster and analyses. Criteria for choosing the proper Carbopack support were outlined. Numerous new organic polymer supports were examined and evaluated for use in specific applications. A copolymer of tetrafluoroethylene with ethylene of equimolar composition was synthesized (270) and employed for separating alipathic and aromatic hydrocarbons, oxygen-containing substances including free acids. Also, the suitability of using polycaprolactam as an adsorbent for separating aromatics and alcohols was studied (210). The results were compared to those obtained on columns packed with 10% Reoplex 400 on Celite. Schuchmann (280) described coating of a synthetic solid support Volaspher A2 with a liquid stationary phase. Suzuki et al. (250) studied the hydrophilic-hydrophobic character of the polymer-surface structure of a physical blend of poly(ethy1ene oxide) with polystyrene by inverse gas chromatography. They observed that the island phase separation occurred at a composition larger than 30%. The smaller morphological, sea-island phase change occurred around 50% of polystyrene concentration. These morphological changes in the polymer surface were probably due to the difference in the surface tension between poly(ethy1ene oxide) and polystyrene polymers. Poly(phenylquinoxa1ine) ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
177R
GAS CHROMATOGRAPHY
can be used for GC separation and determination of aldehydes, free fatty acids, amines, and aromatics (200). Amine and ethanolamines are determined directly in model aqueous solutions or in waste waters. Macroporous sorbents were used as packings in high speed separations of nitrogen, carbon dioxide, and ammonia employing very short columns (190). Study of the system consisting of poly(ethy1ene oxide)-ndecane showed that adsorption of the probe at the various interfaces is never negligible. Reliable values of the degree of crystallinity may be derived from measurements. The sharp increase of the Vgowas observed a t 42.3 and 51.4 "C, which is related to the chain unfolding in the crystalline lamellas (100). A method for determination of gas permeability coefficients of polymer membranes under steady-state conditions was described (170). Mathematical models of permeation cells with mixed chambers and concurrent and countercurrent flows were discussed. DiPaola-Baranyi (60) characterized self-consistent polymer-solute and polymerpolymer interactions for polystyrenes, poly(buty1 metacrylates) and their mixture by means of inverse gas chromatography. The miscibility of the blends toward various classes of probes could be quantitatively predicted from the properties of the parent homopolymers. Polymer compactibility increases with decreasing molecular weight. Anhang and Gray (30)developed a method to characterize polymer surfaces according to the differencial free ener y charge associated with the adsorption from the vapor p! l ase of a suitable probe, namely a CH segment of the n-alkane chain, at effectively zero surface coverage. The method is restricted to polar or crystalline polymers, where the n-alkane does not penetrate the bulk of the material during measurements. The two best Russian supports-Chromaton N Super and Chromaton NAW-were studied for adsorption activity by using solutes with different polarities and molecular structures. The experimental data indicate the presence of specific adsorption sites on the silanized support surface while free hydroxyl groups were eliminated. Metal cations seem to be the active sites (130). The most porous polymeric sorbents, GDX-203 and GDX-101 that are made in China, were studied (50). The retention times depend on the sample volume and carrier gas used. When the injected volume is smaller than 0.1 mL, the retention time is related to the slope of the isotherm of the stationary phase. Olefiis can be subtracted from aliphatic and aromatic hydrocarbon mixtures by means of porous sulfonated ion-exchange resins (240). Their advantages over sulfuric acid columns were discussed. Applications of selective complexation by an europium(II1) coordination polymer sorbent for the prefractionation of volatile compounds such as urinary metabolites and gasoline decomposition products was described (180). Takahara et al. (290) sorbed free fatty acids from air by alkali beads. The efficiency was >go% for Cz-C6 fatty acids at low concentrations. Ito (120) reviewed the determination of physical properties and molecular structures of various polymers by using inverse gas chromatography. Modified alumina surfaces, pretreated with heat and subsequently coated with various amounts of KzC03,were studied. The salt loadin dependence of the specific surface area of the modified atfsorbent could be approximated as a linear relation (16D). Lithium aluminates were patented (40) as substrate modifiers for the GC of aliphatic and aromatic hydrocarbons and halocarbons. Hillerova et al. (110) measured the surface polarity of peptized aluminas using differences between benzene and n-heptane chemical potentials. The polarity decreased in relation on the peptization agent used in the order HF > HC1> H2S04> none > NaOH. The alternative method, measurement of polarity by reluctance of the surface to nonpolar alkanes, was found unsuitable. The adsorption of alkanes, chloroalkanes, and benzene or iron(I1) sulfide was studied at 333.2-433.2 K. Distribution coefficients and associated thermodynamic parameters indicate surface heterogeneity due to the presence of oxide impurities. This heterogeneity and low adsorption capacity make FeS unsuitable for analytical pur oses. Adsorption properties of FeS were compared with t ose of mercury and molybdenum sulfides (70). Adsorption isotherms of n-alkanes and polar adsorbates on short glass fibers were determined for use in the reinforcement plastics (220). The isotherms were well described by the BET equation. The London dispersion force contribution to the
R
178R
ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
surface free energy of the fibers was 50 f 6 mJ/m2, while the specific interaction contribution to the work of adhesion of benzene to glass fibers was 16 f 2 mJ/m2.
SORPTION PROCESSES AND SOLVENTS Research in the properties and mechanisms of absorbents and catalysts continue to be an area of active research. The effects of the substitution of Y-type zeolites by other alkali metal cations were studied on the adsorption-chromatographic properties, especially on the retention of Xe, Kr, Ar, oxygen, carbon-dioxide,carbon monoxide, and nitrogen by the zeolite ( I E ) . Also natural zeolites from various U.S. deposits were evaluated as packings for a GC column used to separate the components of a Hz, 02,Ar, N2,Kr, CO, and CH4 mixture. Columns packed with chabazite produced a complete separation of six components. Oxygen and argon pair was not resolved. Columns packed with ferrierite produced the same elution sequence but achieved only partial separation of Kr and CHI. Columns packed with erionite induced incomplete separation of Kr, CO, and CHI. Mordenite yielded an elution sequence of CH4,Ar, 0 N2, and CO with incomplete separation of CH4, Ar, and The H2, Oz, Ar, N2, Kr, CO, and CHI mixture underwent no separation in columns packed either with phillipsite or with clinoptilolite (3E). The adsorption of toluene on H-mordenite under reaction conditions was studied by a pulse chromatographic technique (13E). Avgul et al. (4E) investigated the adsorption and GC properties of split graphite. The methanol adsorption isotherm is concave in relation to the adsorption axis, owing to hydrophobicity of the surface. The adsorption heat of isooctane on split gra hite increases as the filling up of a monolayer is enhanceidue to its uniform surface. The split graphite can be used for separating geometrical and structural isomers. Kiselev et al. (16E) studied the role of nitrogen atoms in various valence states on the absorption of nitrogen-containing compounds on the graphitized thermal carbon black. GC was applied to determine the thermodynamic characteristics of adsorption. The logarithm of the retention volumes and the heat of adsorption of n-alkylamines and n-alkylnitriles linearly depend on the number of carbon atoms in the molecule and on the average polarizability of the molecule. A relation was established between the thermodynamic parameters and the geometry of the molecule on the graphitized thermal carbon black surface. Similar data were presented by Stukelman on graphitized thermal carbon black (23E). Adsorption of amino acid derivatives on graphitized thermal carbon black surfaces was studied by gas chromatography at 120-260 "C (26E). It was observed that graphitized, hydrogenated thermal carbon black can be used for the separation of amino acid isomers. Another study of adsorption from a binary mixture with an ultimately small content of one component employing graphitized carbon black or silochrome coatings was studied (68). Charcoal samplin of N,N-dimethylformamide in air Samples from a polyuret ane plant was performed by drawing air through a sampling tube at 0.1 L/min and by determining organic vapors spectrophotometrically at 215.4 nm. The presence of other pollutants did not interfere (20E). Several fundamental studies have been reported on aluminum oxide, silica gel, aluminum silicate (5E),magnesium oxide, and magnesium carbonate (17E). The thermodynamic characteristicsof the adsorption of individual CB-alkylbenzenes on organo-substituted layer silicates were also studied (7E). It is shown that depending on the type of modifying cations, the selectivity of organo-substituted layer silicates is determined by either the enthalpic or the entropic component of the Gibbs free energy change. Hydrocarbons were employed for assessing the selectivity and determining the thermodynamic characteristics of adsorption on the organo-substituted layered silicates (27E). In case of highly dispersed silicates the selectivity of the sorbents, and in the case of vermiculite, the column efficiency, affects the separation. The minerals exhibiting a lower layer charge density than that of vermiculite are expected to behave as selective sorbents. Cuprous chloride modified diethyleneglycol succinate stationary phase greatly improves resolution for high-boiling olefins (24E). Siu et al. studied the effect of adding small amounts of trifluoroacetylacetone to the helium carrier gas on the separation of the trifluoroacetylacetonates of Cr(II), Al(III), and Fe(II1). Igarashi and Ogino (14E) presented details of a high-
6,.
!i
GAS CHROMATOGRAPHY
pressure microcatalytic pulse reaction system equipped with a high-pressure GC. This reactor allows one to measure the activity of any desired catalyst at C550 "C and C100 atm. A similar system was described by Mihaila et al. ( B E ) . Pulse flow GC technique in heterogenous catalysis was employed by Giordano (9E).The isoteric heat of adsorption of CzH4 on 7-AlZO3is 8.8 kcal/mol as compared to 5.8 kcal/mol for adsorption of CzH4 on SiO2.A1,O3. Irreversble adsorption of ethanol occurs on 7-A1203. Katsanos determined the rate constants of surface-catalyzed reactions (15E), in columns containing the catalyst. The mathematical expressions describing the elution curves when the gas flow is reversed were derived for a general case and then applied to two specific reaction schemes. By plotting the logarithm of the area under the extra peaks as a function of time, the rate constants of the surface steps of the reaction were determined. In another work (19E), the nonlinear dependence of V," on volume of liquid phase, VL, was studied on a series of volatile organic compounds with 4-propylphenol as the liquid phase on a solid support. In reaction chromatography, porous styrylboronic acid polymer beads can be used as subtractors for alcohols (IOE). The deteriorated subtractor can be regenerated by HC1 treatment. Primary and secondary amines can be subtracted on the porous maleic anhydride-divinylbenzene copolymer beads. The preparation procedure is described in detail (11E). Tertiary amines, hydrocarbons, ethers, ketones, aldehydes, alkylhalides, mercaptans, esters, and epoxides were not subtracted. Calculation of breakthrough times by means of the applicability of a semiempirical absorption model to the absorption of binary mixtures on active carbon was described (12E). Breakthrough times can be calculated from experimental peak heights and peak migration velocities for both components. The effects of various parameters on peak heights and migration velocities were discussed. Selim et al. (21E)used the mass spectrometric tracer pulse chromatography technique to measure the equilibrium isotherms of acetone with hexadecane coated on different chromatographic supports. A model was proposed and shown to be accurate for these systems. The model is based on the assumptions that total adsorption represented a sum of the liquid and solid contributions, that the mechanisms operate independently, and that there is no measurable liquidaurface adsorption at these temperatures and pressures. Anhang et al. (2E)measured GC retention of a series of n-alkanes at effectively zero coverage on a poly(ethy1eneterephthalate) film surface. The free energy of adsorption per CH2 segment of n-alkane at zero surface coverage was calculated. This value is a direct measure of the London nonpolar interactions of the surface. The method is restricted to polar or crystalline polymers where the n-alkane does not penetrate the bulk of the material during the measurements. Gawdzik et al. (823)used a cross-linked porous styrene for the separation of various classes of organic compounds. Its properties were compared with those of Chromosorb 101 and Poropak Q. The new column packing could be used for separation of amines. The thermal degradation products of polyethylene (450-526 "C) especially a liquid fraction formed over a SiOZ-Alz0, catalyst were studied (25E) by WCOT column GC. The liquid fraction contains large amounts of the same isoalkanes and aromatics present in the gasoline fraction of petroleum. Most of the isoalkanes are monobranched with a methyl group at the 2- or 3-position. The aromatics consist mainly of those with more than one methyl group. Isomerization, aromatization, and hydrogen-transfer reactions seem to play an important role in the secondary degradation of the primary products of polyethylene.
OPEN TUBULAR COLUMN GAS CHROMATOGRAPHY Theory and Techniques. The present state of open tubular column (OTC) gas chromatography has been reviewed ( I O F ) . It covered recent developments in the preparation of glass OTC's with special emphasis on physical problems to a glass-type, nature of the stationary phase, surface modification, and type of substance analyzed. Olsen (30F)presented a review describing the processes by which the immobilization and crosslinking of a stationary phase occurs. Calder (6F) described a simple method for sealing the ends of fused-silica
capillary tubings, where a 2-cm length of protective polyimide coating is removed by heating with a microburner. A 3-cm long Pyrex glass collar is slipped over the silica tubing and fused to the first 1.5 cm of exposed surface so that the collar is flush to the end of the fused-silica tubing. After filling the column, an end seal is achieved by connecting a glass plug to the collar with silicone rubber tubing under ethanol. Another technique is using paraffin (at 50 "C) or silicone rubber (at 20 "C). The solvent-paraffin (silicone rubber) meniscus is moved 1-2 cm by applying low vacuum (0.1 bar) to the opposite end. The plug does not react with the coating solution and it can be removed by heating and applying pressure at the opposite end (19F,41F). A revised, comprehensive description for preparation of inert glass OTC columns was presented (11F). A review with 29 references describing preparation of glass OTC's was presented by Herilier (16F). Conditions necessary for producing good glass WCOT columns were outlined and procedures for glass surface modification and stationary phase deposition were described in detail. The tailing of peaks of C, and C8 alcohols on thermally aged fused-silica WCOT columns was minimized by deactivating the inner wall by injecting 4 pL of propylene glycol in splitless mode at 250 "C for 1 h and maintaining the column at 250 "C overnight (28F). Base-line drift due to exponential increase of bleeding from the stationary phase was compensated by using a voltage in the automatic linear temperature programmer to cancel drift when fed into the electrometer (2F). Garbuzov et al. (9F)discussed the outer column peak broadening, the value of which coincided with the sum of the characteristic times of the used apparatus and the time of sample introduction. The broadening, which is not accounted by the Golay theory (1980), is related to the mass transfer which occurs in the mobile phase as well as the stationary phase. Further experimental work with turbulence amplifiers as sample injectors and stream switches in chromatography was reported by Annino and Leone ( I F ) . A newly designed system with two logic gates functioned satisfactorily as a dual valve for the alternate injection of sample and standard. In addition, an ensemble averaging technique for signal enhancement was found to be less sensitive to operating parameters than correlation chromatography. Saito (34F) evaluated high purity fused-silica capillaries made of 99.9999% SiOz for GC. Untreated fused-silica OTC's were compared with those deactivated with PEG-2OM and those coated with OV-101. OV-101 treated capillaries showed some activity after coating but after conditioning at 280-350 "C, they showed almost the same degree of inertness as the deactivated columns. Grob (12F)studied "band broadening in space" and the retention gap in OTC chromatography. It occurs during splitless injections with the solvent effect and cold on-column sampling. It is assumed that this is due to partial transport of the solvent within the flooded zone by the vapor phase. Minor temperature gradients in the column inlet may greatly influence the peak distortion. The retention gap is proposed as a method of eliminating peak distortion caused by band broadening in space. The peak broadening is reduced by a factor corresponding to the reduction of the film thickness in the retention gap zone compared with the remainder of the column. The same author studied dependence of the splitting ratio on column temperature in split injection mode. The amount of sample entering an OTC during split injection increases considerably if solvent recondenses in the column inlet. The resulting splitting ratio may deviate from the preset ratio by a factor greater than 30. Recondensation occurs at column temperatures below the boiling point of the major component. The deviation of the preset splitting ratio is an important source of error in quantitation based on the external standardization (13F). Olacsi et al. (29F)derived a formula for determining the film thickness in WCOT columns. Optimization of experimental conditions for the analysis of complex mixtures was attempted (24F),and a WCOT column prepared by connecting two different polarity columns was suggested for separatin PCB congeners. It appears possible to determine the seconcf virial coefficient, the viscosity at zero pressure, and the pressure dependence of the viscosity of gases and gas mixtures by varying the pressures at both ends of a OTC (17F). Influence of a sophisticated cold trap on the shape of chromatographic peaks was studied in detail (4F,1 5 0 . ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
179R
GAS CHROMATOGRAPHY
Graydon et al. (14F) evaluated the efficiency of capillary cold traps immersed in liquid nitrogen. The results on a standard mixture showed poor recovery of the most volatile components. Breakthrough was most pronounced during the first moments of trapping and was followed by a rapid increase in trapping efficiency. Chemistry of siliceous capillary OTC‘s was studied by Wright (42F). A novel approach for cross-linking of alkylpolysiloxane films on various types of glass surfaces including fused silica using y-radiation of a cobalt-60 was employed and results were compared to those obtained by the thermal peroxide treatment by Schomburg et al. (35F). The films are immobilized against solvent rinsing by using methylene chloride, pentane, and acetone and maintain homogeneity at high temperature. Various doses of y-radiation from a cobalt-60 source were used for the cross-linking instead of the thermal peroxide treatment. By y-radiation no polar functional groups are introduced into the stationary phase. Less than 20% of the various residues are usually removed from the OTC’s by solvent rinsing. This technique has also been employed commercially. Lipsky and MacMurray (25F) assessed the chromatographic performance of different types of cross-linked methylpolysiloxane stationary phases on fused-silica OTC’s. Columns showing excellent efficiency, thermal stability, and persistance to certain solvents were prepared from both classes of polymers having either SiOSi or SiCSi cross-linkages. Renewed surface activity is showed on fused-silica columns cross-linked with peroxides. This effect was either minimal or absent when the reactive prepolymers were cross-linked with tetrachlorosilane. Diez-Masa et al. (7F) described a method for bonding silicone phases on the inner wall using ammonia-nitrogen mixture at 340 OC for 2 h. Tersac (38F) prepared a polyaryl pyridyl ether thermostable stationary phase which can be used at temperatures greater than 205 “C. Vinet (40F)deactivated his columns with OV-17 at 399 “C under a low flow of nitrogen and afterwards they were conditioned with vapors of phenyldiethanolamine succinate added to the carrier gas stream by bleeding it from a coated injector glass tube. Determinations of tricyclic antidepresanb in plasma with such OTC’s result in a low relative standard deviation and a linear calibration curve, reflecting the effectiveness of the deactivation. Coating with intermediate polymer layers significantly improves the efficiency and reproducibility of copper alloy OTC’s. Best results were obtained with polymer layers containing finely dispersed mineral fillers (20F). Use of packed capillary column is finding some applications in rapid analysis (3F). The chromatographic analysis of 4-12 component mixtures of hydrocarbons and chlorinated hydrocarbons was carried out within 2-5 min on a 3 m X 0.8-1.5 mm i.d. packed glass or stainless steel columns packed with packings havin particle sizes from 0.1 to 0.25 mm. Kocsi et al. (21F) descrited their method for the preparation of graphite-coated OTC’s. Graphite was formed by thermal degradation of methylene chloride at 773 K. Performance data were given for columns coated with various phases. Metallic OTC can be prepared by coating capillary walls with aerosil treated using silanizing agents. Pyrosilica is formed during the combustion of silicone oil vapors in a hydrogen flame. The cement formed was then dried to a constant weight at 400-450 OC (338‘). Traitler and Rossier (39F) studied the influence of some inorganic salts such as NaF, NaC1, NaBr, and silver nitrate on the polarity of OTC’s. The polarity is reflected by a better resolution and shorter retention time of &/trans isomers of fatty acid methyl esters and positional isomers of triglycerides. It has been shown by Schutjes et al. (36F) that speed of analysis in isothermal and temperature-programmedOTC-GC can be reduced significantly be reduction of the column diameter. With 50-pm i.d. columns coated with nonpolar stationary phases, plate numbers between 100000 and 1000000 theoretical plates were obtained. Several examples of highspeed, high-resolution analyses of complex samples were presented. Janssen et al. (18F)developed a method for the in situ coating of an OTC with a high-temperature nematic liquid crystal, N,”-bis(p-phenylbenzylidene)-a,a’-bi-p-toluidine,as a stationary phase. The reaction components, a,a‘-bi-ptoluidine and p-phenylbenzaldehyde were brought together in the OTC and reacted with each other during the evacuation step in the static coating technique. 180R ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
Onuska et al. (31F) developed an integrated analytical procedure for polychlorinated biphenyl multiresidue analysis in environmental samples. PCB residues were characterized and quantified by WCOT column GC using electron-capture detection. An automated data system was used to select and quantitate peaks of individual isomers, homologue groups of PCB’s, and total PCB. The procedure consistently yields results with reproducibility within 3%. Bush et al. (5F) proposed mixtures of various Aroclors as a universally applicable calibration standard for analyses of environmentally modified PCB’s at ng/g level. The first reported separation for transition-metal porphyrin complexes containing a closed macrocyclic ring by GC was reported by Marriott et al. (26F). Kovats retention indices are in the range of 5200-5600 necessitating the use of short OTC’s. For aetioporphyrin 1, complete separation of Cu, Ni, Co, Pd, and Pt complexes is possible, but with octaethylporphyrin the Ni and vandyl complexes are incompletely resolved. The forensic analysis of street drugs on a cross-linked SE-52 fused-silica OTC was described (32F). Chlorinated methyl propenoates were separated by OTC on the SE-30 and the highly polar OV-351 stationary phase under the same operating conditions. The retention data for the compounds at isothermal and prograpned column temperatures are given and the elution order is discussed. Separation of diterpene acids on OTC’s of different polarity was performed and the advances of a column coated with FFAP for the separation of crude and distilled tailoil and fatty acid samples were discussed (27F). Separation of homologous series of halogenethyl esters of alipathic monocarboxylic acids on OV-101 WCOT column was studied (22F). Shimizu (37F) evaluated the effect of make-up gas on chromatographic peaks in GC/MS. Increasing make-up gas under a definite carrier gas pressure decreased the gas velocity, increased analysis time, improved the peak resolution, and decreased the peak sharpness.
INSTRUMENTATION The number of papers cited in this review, describing improvements in WCOT column GC instrumentation, indicate the high level of interest in building systems around a microprocessor. Ahlstrom (16)patented a repetitive chromatographic system which employs a backflush valve downstream from the detector and a separate sample injection valve located directly upstream from the chromatographic column. The type and location of the sample valve and the backflush valve allow continuous monitoring of a sample system. The apparatus is particularly useful for rapid on-line analysis for trace amounts of water in organic streams containing HCl and or c1. A new method, derived from GC with backflushing was described (5G). It is a two-step method-isothermal during the first step and then, the gas flow is reversed and a temperature programmed cycle included in the backflushing step. Volatile solutes are eluted during the forward direction of the carrier gas in the usual way, while high-boiling components are backflushed. Guillemin (22G) described computerized autocontrol of on-line or laboratory GC’s. It can be achieved by computerizing the interpretation of some chromatographic quantities for the deferred standard such as peak area, peak height, and retention time and can discriminate among the sample injection, the separation, or the detection systems as sources of problems. An integrator, in addition to quantitative information, can display messages about the status of the chromatograph. This permanent autocontrol system should be an integral part in a closed-loop control of a modern process GC system. A similar system was described in (68G) and (35G). A review discussing data handling in GC was published by Koskinen (38G). Some problems of real-time data processing in quantitative GC analysis by means of a digital computer were studied (6G). The smoothing of data, the detection of the peak, and the evaluation of integration and base-line correction and the method of handling some irregular peaks were discussed. Results of the tests of real-time data processing were given. In aham et al. (29G)presented a series of computer-constructefvan Deemter curves that permit evaluation of a number of variables in OTC-GC. The graphs permit the comparison of interrelated parameters, including
GAS CHROMATOGRAPHY
the choice of carrier gas, column length, column diameter, solute partition ratios, and stationary-phase film thickness. The curves were evaluated both in terms of the relative magnitude of the optimum average linear carrier gas velocity and in terms of the significance of the sharpness of the curve. A very effective utilization of microprocessors can be applied for the automatic generation of a starting electrical signal during the injection of a liquid or gas sample into a GC (33G). The piston of the syringe is attached to an adapter with a permanent magnet attached to its side. The length of the magnetic relay is fixed in such a way that when the total volume of the sample in the syringe is injected, the permanent magnet and the relay come exactly opposite each other, and the starting electrical signal is generated. A versatile, microprocessor injection system for OTC was developed for incorporation into gas chromatographs not possessing capillary column valve switching capabilities. This system incorporated splitless and preconcentration injection techniques allowing for injection of large volumes of sample but bypassing excess solvent and column residue. By microprocessor-controlled valving sequences, the injected sample was transferred onto the OTC and the injector space was purged of residual solvent and sample, while venting the system and supplying make-up carrier gas to the detector (47G). Tschida (43G) described a pattern recognition technique for identification and quantitation of complex mixtures and elimination of interferences by simple programming techniques. The method is illustrated by identification and quantitation of some polychlorinated biphenyl mixtures. Theory and applications of GC headspace analysis were reviewed (34G) and improvements relating to headspacesampling apparatus were patented (7G, 9G). An automatic, electropneumatic sampling system was used to remove aliquots of a typical fermentation headspace gas over 6-min intervals. An external standardization was selected to determine the ethanol concentration in the gaseous and hence liquid phases. The head-space peak area was linearly proportional to the liquid phase ethanol concentration over the ran e of 2-80 mg/mL (8G). New applications for headspace 8 C in agricultural and polymer degradation research were described (11G). Specific examples were drawn from various forms of headspace analysis with emphasis on the automated static equilibrium method. A rapid method for using a headspace sampling technique and GC detection was developed (27G) for the analysis of ethanol in canned salmon. The highly significant correlation between the ethanol content and the sensory classification of decompositionin canned salmon found in previous work using different analytical methodology was confirmed in this study. The use of headspace GC with three different injection systems and various separation systems for routine monitoring of volatile organics in industrial wastewaters at mg/L to pg/L levels was described (45G). Automated headspace GC for identification of bacteria in clinical microbiology and diagnosis of bacterial infections based on detection of short-chain fatty acids produced was described for the diagnosis of septicemia by using human blood cultures and the diagnosis of intraabdominal infections by using specimens and the identification of urinary tract pathogens (42G). The double-sampling method of quantitative headspace gas was evaluated by Drost and Novak (13G). Model water-gas systems with benzene, toluene and ethylbenzene, n-decane, and n-dodecane gas as analytes were employed. In this technique two headspace samples were withdrawn successively from the system and analyzed by GC. The total initial analyte content of the system was calculated by virtue of the concentration decrease in the gaseous phase brought about by the withdrawal of the first headspace sample. Combined with Grob’s closed-loop strip/trap technique, the method provides for the determination of concentrations of the above hydrocarbons in water with an average relative error of several percent. For older GC instruments as well as for improving newer equipment, a combination syringe needle guide and septum purge adapter was designed (10G).It was used with fusedsilica OTC’s with subambient column temperature programming and high detector sensitivities. Greatly enhanced septum life and easier injections are other benefits. Laine (4113) gives details of a schematic diagram, showing the mode of connecting four six-port valves which result in a system suitable for study of both reaction and adsorption phenomena in
continuous and pulse modes. The system can be used in conjunction with computer automation to control actuation of the valves, perform calculations involved in analysis, and modify operating conditions. The system can also be used to study catalyst poisoning and other catalyst changes. Scott (59G) reviewed the history of the development of the GC WCOT columns. Smith (60G)described a simple device for straightening the ends of glass WCOT columns. Method and apparatus for degassin liquids with dissolved gases was patented by Hiraizumi fh6G). Liquids containing dissolved gases were degased by being placed in a plastic container at a reduced pressure. The system is suitable for degassin of solvents for liquid chromatography. A method was descrited for the continuous biological monitoring of the effluent from a high-resolution GC column using a single-cell recording technique (652). The system can be used to provide precise information on the retention times of compounds with olfactory activity that are not detected with a coupled GCelectroantennogram system. The Grob (1969, 1972) sample injector which permits both split and splitless in‘ection can be fabricated by modifying a commercial packed-column injector body (15G). Performance is excellent and the cost is very reasonable. Modifications were made on Varian splitless injector for OTC’s to reduce the dead volume and thus improve the performance of the injector. The improved modification allows the introduction of a sample into a closed and evacuated volume. The vaporization process is hampered by an initial pressure. The injector is operated in three sequential modes: evacuation, sample loading, and injection (23G). Schomburg et al. (58G) investigated a new sampling technique for WCOT column GC, which combines the advantages of split sampling, on-column, and cold injection techniques, respectively. The liquid sample was introduced into a short precolumn coupled to the main WCOT column. The vaporized sample was separated into different peak groups, within the precolumn, and they were then transferred to the split region of a low dead volume T-piece located between the precolumn and the WCOT column. The application of the split-splitless injector containing a trap resulting in a 10-500-fold increase in the overall sensitivity to environmental analysis was described by Vogt et al. (64G). The solvent is vented prior to the separation step so that the column is protected from washing out effects. Various standard and environmental samples containing organochlorine or organophosphoruscompounds were analyzed. Comparable performance with the conventional split technique with higher sensitivity is achieved. Bayer and Liu (4G) observed that the main sources of discrimination in split injection arise from the change in the splitting ratio. It is caused by variation in the composition of the gaseous phase and nonuniform distribution of the solvent in the total gaseous sample plug formed during evaporation. Taking this into account a new split injection technique, characterized by interruption of the carrier gas flow during the sample evaporation period, was developed whereby the formation of a sample plug was enhanced. Sisti et al. (60G) patented a method for the controlled and reproducible introduction of very small amounts of a liquid sample (10 pL to 50 nL) into a WCOT column and TLC plates. The equipment consists of a sample container with a pipet-like outlet. The sample is submitted to at least one pressure plate which is controiled in time or amplitude to allow drawing a controlled quantity of liquid form the outlet. An on-column injection device was described (66G, 67G) which utilizes a septum and can be adopted to any commercial GC. It permits the introduction of relatively large sample volumes (greater than 10 pL) and can be performed at elevated temperatures. Takayama (62G, 63G) described a natural cooling system for WCOT columns in which the injection point on the column is cooled outside the oven. Sample discrimination in the tip of the syringe needle is eliminated by using this natural cooling system. When the syringe needle is inserted into the column, the section of the column which includes the injection point is withdrawn from the oven and is kept at room temperature. Rothchild et al. (56G) subjected a narrow well-defined region of the column to cooling with liquid carbon dioxide. Efficient cryofocusing of the desorbed sample is achieved. A cooling-expansion jacket for the WCOT column was constructed by modifying a l/ls in. Swagelock-typemetal tee. ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
181 R
GAS CHROMATOGRAPHY
Quantitative routine analyses of technical pesticide Baycor were performed by using WCOT columns and the on-column and split sampling. The standard deviations of the relative response factors were strongly dependent on the type of solvent. With on-column injection a t 40-50 "C, relative standard derivations of the relative response factor were better than 1%, independent of solvent volatility (54G). The lowpressure gas injection device was described by Gauthier (19G) and a desorption-injection system providing a convenient means to transfer preconcentrated volatile samples from a sorbent trap onto a GC column without interruption of the operation was evaluated by Purcell et al. (55G). The design of a septumless injector for WCOT columns was described, and the chromatogram obtained when using an injection port was compared with that of septumless injected. The described septumless injection port eliminates septum bleeding without deterioration of the chromatographic performance (21G). Modification of the septum holder and injection time role were described (36G) to improve the results of the inlet splitter injector. A pneumatic sample inlet system was developed (31G ) for automatic variation of vapor concentration. Pneumatic resistance is automatically adjusted to match that of the columns so that flow switching creates negligible disturbance. The system, consisting of a six-port regulating valve, can handle a wide range of solute concentrations and thus measure complete isotherms conveniently. The power of WCOT column GC can be enhanced by selective fractionation of the sample. A modification of a commercial instrument for heart cutting from a packed column using an automated Deans switch and an electrical heated trap is described (53G). Benefits are illustrated with chromatograms of naphtha, urinary aromatic acids and wine volatiles. Systematic errors occurring with the use of gas-sampling loop injectors were investigated (30G). Adsorption of the solute on the inner wall of the loop causes a systematic error in the injected amount. This effect can be significant as is shown by experiments and theoretical calculations. Some of the most recent advances in the GC/Fouriertransform infrared (FTIR) software and hardware were described by Krishnan et al. (39G). A powerful software routine for the collection and analyses of GC/FTIR data was discussed and some results with WCOT columns were presented. A dedicated low-volume, short-lightpipe cell was developed as an interface for HRGC FTIR. A routine operational level of 100 ng is claimed (57 ) for general applications. A similar interface was described (61G ) . Excellent chromatographic resolution, low-nanogram sensitivity, and compound identification were demonstrated. A vapor-phase library search system is used to identify unknowns. An economical HRGC/FTIR system was applied to isomer identification, fragrance analysis, and petrochemical analysis (I8G). This technique was satisfactorily used to identify monoterpenes in commercial products and plant extracts (44G). Element and isotope specific detection of HRGC MS using a microwave discharge interface was employed etween a WCOT column GC and low-resolution mass spectrometer to convert eluting organic substitutes to common di- and triatomic molecules to enhance the detection of isotopes without destroying chromatographic resolution (48G). The possibility for the combination of GC with a microwave induced plasma showed that detection limits down to the picogram range can be obtained (2G). Element-specific detection for HRGC separation of Ge, Sn, and Pb tetraalkylorganometallics was carried out by microwave-induced and sustained helium plasma atomic emmission spectroscopy utilizing the TMolo cavity (16G). A sequential determination of chromatographically separated hydrides was demonstrated by means of a sequential slew scanning monochromator as a plasma emission chromatographic detector (14G). The detection limits claimed are 4 ng for Ge and 50 ng for As and Sb. Relative standard deviations at the 1-pg level range 2-5%. Accuracy was demonstrated by analyzing EPA water quality control reference standards. The low-power Ar/Ar and the high power N/Ar plasma were compared under conditions of routine analyses. Some advantages of the nitrogen-cooled plasma were discussed, such as application to organic solvents and the resulting increase in sensitivity by using higher power input. A sample introduction technique of using a graphite crucible which is inserted directly into the plasma was described. Trace analyses of small amounts of liquid and solid
b
b
182R
ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
samples seem to be possible using this technique (52G). Among various detection systems, applications of common-type electron-capture detector in HRGC were reviewed (28G). The most sensitive compounds are derivatized iodothyronines which are essentially 20-fold more sensitive than lindane. N,N-di(pentafluorobenzoyl)pentafluoroaniline,a somewhat less sensitive but more volatile substance, was selected for determination of a detection limit. The value was 90 ag (1.6 X mol). This increases the reported sensitivity of GC-ECD by 100-fold (9G). A microprocessor-controlled ion mobiljty detector specifically adapted to the detection of components separated by HRGC was described by Baim et al. (3G). Results obtained from the nonselective and selective detection of components of an orange extract separated by WCOT column illustrate the various operating modes of the detector. Green (20G) reviewed the most promising approaches for coupling laser spectrometry with gas and liquid chromatography. A chemiluminescent nitrogen detector was constructed and applied to measurement of atmospheric ammonia and amines (32G). A xenon ionization detector was used in computed tomography scanners. Its suitability for digital radiology was tested (I2G). Heil (25G) described a parallel plate avalanche chamber to observe nuclear disintegrations. A PPAC prototype was designed with 90% efficiency, 3-11s jitter, 2-nsrise time, 20 mg/cm2 mass, and 1.5-mm special accuracy. The parameters studied were electrodes design, choice of gas fill, electronics, and anode strips. The detector is to be used as a hodoscope with high flux of particles. Reactant ion monitoring in GC-chemical ionization mass spectrometry (GC/CIMS) analysis was described (51G ) . The Hewlett-Packard 5993 B GC/MS system was evaluated according to the procedures found in EPA research report number EPA-600/4-80-025 ( I 7G). The system performed satisfactorily during the evaluation and is acceptable for the analysis of organic compounds. Both mass spectral library searches were accurate. Test and performance of a GC/MS interface with a fused-silica transfer line was described (40G). The interface was tested with different substances for catalytic decomposition, adsorption, and sensitivity toward acidic and basic compounds. Use of a GC/MS-computer system in toxicological analysis was described (46G). Automatic determination of C2-C5 hydrocarbons in the air by using a flame ionization detector coupled with a microprocessor was described by Hanai (24G). Water corrosion studies of aluminum alloys were performed (50G). The sensitivity of a GC is monitored by periodic introduction of a standard substance into the carrier gas stream. The process is simplified by combining the operations of preparing and adding the standard and by continually passing a moist carrier gas through an electrolyzer in which water is absorbed from the carrier gas and periodically electrolyzed to hydrogen and oxygen. These gases are used as the standard substances (37G).
HIGH-RESOLUTION COLUMNS AND APPLICATIONS There have been a number of publications reporting the preparation of WCOT columns or discussing novel studies of OTC's durability, thermal stability, inertness, and crosslinking. Some new advances were summarized at the International capillary column symposium held at Riva del Garda (42H). A comparison between capillary and high-resolution gas chromatography was made in terms of performance and efficiency (38I-I). A compact description was given of a simple and reliable method of drawing fused-silica tubing (3123. It was emphasized that the practice of drawing optical fibers could lead to complicated and expensive equipment. Satisfactory fused-silica tubing can be made with extension of the method developed earlier for drawing thick-walled capillaries. A simple hydrogen-oxygen flame burner was described for fusing the preformed tubing at the draw point, which is enclosed by a water-cooled glass enclosure to trap evaporated silica and maintain the operation under dust-free conditions. The uniformity of the capillary diameter is better than 5%. Zlatkis (41H) described development and fabrication of fused-silicaWCOT columns, which were used in the trace gas analyzer for the space shuttle and were coated with polyoxyethylene lauryl ether. This stationary phase is of medium polarity and has a temperature limit of 160 "C. Column characteristicsaffecting the chromatographic behavior of glass
GAS CHROMATOGRAPHY
and fused-silica WCOT columns include the dimensional uniformity of the OTC, the physical and chemical characteristics of the column wall, and the characteristics of the stationary-phase film, which are the most important criteria affecting column reproducibility (21H). Tesarik et al. (35H, 36H) studied preparation of soft-glassWCOT columns. They were etched by HF released from the trifluoroethyl ether vapors a t different temperatures, Maximum efficiency was obtained after 3 h a t 423 K. The effect of wall coating conditions in the static pressure method (Ilkova, Mistryukov, 1971) on the separation efficiency was also studied. The column efficiency was most affected by the temperature of the coating oven (403-453 K); the concentration of coating solution had little influence (0.2-0.6%) and efficiency was independent of the velocity of the column through the oven (12-48 cm min). The adsorption activity of the inner surface of quartz TC's is low enough to use them for separation of polar organic substances of differing nature (5H). Pretreatment of the fused-silica tubing with Superox-4 increased the surface energy, improved the wettability of the surface for polar phases, and deactivated the fused-silica surface. The polar stationary phases, Superox-4 and SP-1000, were statically coated onto the Superox-4treated surface ( 3 W . Burrows et al. (8H)deactivated OTC's with triphenylchlorosilane and diphenyldichlorosilane or octaphenylcyclotetrasiloxane solutions in methylene chloride. Extended wettability was achieved with diphenyldichlorosilane. Octaphenylcyclotetrasiloxane undergoes ring opening and surface polymerization to give a thermostable layer which effectively shields surface silanol groups, According to Karl et al. (22H) glass alkylation with pentafluorobenzyl bromide yields OTC's with modified retention characteristics. Glass-alkylated OV-225 was tested with pentafluorobenzyl fluoracetate and the substantial increase in retention time of this highly volatile compound improved the precision of analysis. High-temperature silylation of leached glass OTC's is a highly effective deactivation method for preparing neutral and inert surfaces (39"). Several agents such as disilazanes and disiloxanes containing different alkyl and phenyl groups were investigated. By increasing chain length or number of phenyl groups in the reagent, better wettability for numerous stationary phases was observed. A number of factors affecting the distribution of the stationary phase on the inner wall were examined (29H). Adsorption and capillary forces tend to redistribute the stationary phase toward an equilibrium configuration during column conditioning, while secondary effects such as gravity evaporation of volatile stationary phase can create uncovered patches and films of varying thickness. Significant depletion of stationary phase was observed at the inlet portion of the OTC and gravity flow did occur. Buijten et al. (7H) prepared glass OTC's by silanization with hexaphenylcyclotrisiloxane. These ca illaries were well deactivated and readily wetted by phenylsi icone stationary phases. The silanized capillaries were coated statically with 0.5% methylphenylsilicone gum solution in methylene chloride. Tetraphenyldimethylsilazane was used for high-temperature silanization of Pyrex glass OTC's. They were statically coated with a 1:4 (w/w) mixture of FFAP and OV-1 in dichloroetane. The column was used for the analyzing of volatile carboxylic acids (37H). According to Grob and Grob (14H)immobilization of apolar silicone phases is essentially understood and mastered; however, the corresponding treatment of even moderately polar phases remain problematic. Upon initiation by peroxide radicals, these phases respond by forming transformation products rather than by bonding to the support surface or to the neighboring molecules. OV-1701 was the most polar stationary phase which could be reasonably immobilized. Blomberg et al. (623 demonstrated that the combination of leaching, silanziation with cyclic siloxanes, and peroxide-initiated in situ polymerization of silicone stationary phases gives OTC's displaying very high efficiencies,very low absorptivity, and very high stability with low bleeding rates. Such columns have been prepared using AR-glass and fused silica as the supports and SE-30, SE-52, SE-54, and OV-215 as stationary phases. Characterizationof glass, quartz, and fused-silica OTC surfaces was performed by surface wettability measurements (4H). The influence of various surface treatments such as leaching, silylation, and polymeric film formation was discussed. Wettability measurements were also used to evaluate the thermostability of various treated surfaces and to compare
6
P
the surface properties. Characterization of linear and crosslinked polymers such as ethylene-vinyl acetate can be determined by inverse GC using the Kovats index, Rohrschneider constant, and Hildebrand solubility parameters (17H). Determination of surface hydroxyl concentration on glass and fused-silica WCOT columns was performed by exchanging the hydroxyl protons with tritium. Tritium was quantified by combustion to tritiated water followed by scintillation counting (40H). The number of OH groups on a leached hydroxylated Pyrex glass OTC was approximately 2.8 OH groups/nm while an untreated fused-silica had only 0.2 OH groups/nm. Redant et al. (32H) published some observations on dynamic coating of OTC's. Fast drying speeds improve efficiency and increase film thickness. An attempt to optimize a static coating technique involving mechanical closure of the capillary tubing and the principles of the method with a comprehensive description of its application was published by Grob and Grob (15H). A simple method for connecting fused-silicaand glass capillaries by means of a low dead-volume connection was achieved (33H) by modifying the methods of Pretorius (1980) and Lee (1981) and using only polyamide to connect the glass and fused-silica ca illaries. These seals are highly inert, possess minimum ead volume and are stable up to 320 "C at high inlet pressures (100 kPa) and under high vacumn (5 x 10" torr). A method for the concentration and recovery of trace organics in water is based on adsorption on large-bore SE-30 coated columns prior to GC analyses. The results compared favorably with those obtained by headspace nitrogen purging or solvent extraction (18H). The present study demonstrated the use of the p-butoxy homologue and of the liquid crystals N,N'-bis(p-methyloxybenzylidene)-a,d-bi-p-toluidine (BMBT) itself as a stationary phase for separation of PAHs. The influence of surface treatment of the glass wall on column performance was examined (20H) with the effects on selectivity when BMBT is blended with OV-1 or OV-101. Finkelmann and Laub (IOH) synthesized novel mesogenic polysiloxane (PMMS) phases and compared them with those of a poly(methylphenylsi1oxane) gum (SE-52). The former yield high column efficiency commensurate with its gum-like character, yet concomitant high selectivity for positional isomers of methylchrysenes and for PAHs and sulfur containing PAHs. The nematic/isotropic temperature range of the new phase 70-300 "C exceeds by several orders those of previously described liquid-crystal stationary phases. Use of alkylbenzoate esters as stationary phases led to a better separation of the nitrotoluene isomers (12H). The silicone XE-60 was modified by hydrolysis and coupling with L-valine-tert-butylamideto introduce a chiral property and by subsequent chain-opening polymerization with octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane to obtain thermal stability and resolution efficiency (IH).The resulting chiral phase can be used for the separation of amino acid enantiomeric mixtures. The smectic B to smectic E transitions of the reentrant nematic p heptyloxybenzylideneamino-p '-cyanobisphenyl were studied by GC in decaline and napthaline. The reentrant nematic phase has a structure similar to a high-temperature nematic form (24H). Thermodynamics of solution parameters of the isomeric PAHs at infinite dilution in the nematic phase liquid crystal BMBDM [71520-33-71 were determined by HRGC (19H). The unique selectivity exhibited by BMBT toward PAHs is explained from current solution theory in terms of differences in the partial molar enthalpies and entropies of solution. The phenomena created by band broadening in space can be eliminated by the use of a retention gap, i.e., keeping the first 50-80 cm of the OTC free of stationary phase (16H). Several methods for the preparation of a joint between a precolumn and the OTC were discussed. Springer et al. (34H) determined two to four ring PA& with OTCs by using either the split or splitless mode of injection. Both methods of injection gave highly linear responses over the concentration ranges that were studied. The split injection mode was slightly superior to the splitless mode in terms of linearity. The poorer linearity for the raw area data was due to random scatter in the data points, rather than to curvature at either extreme of the plots. Although molecular weight discrimination is less in splitless than in split mode injections, the data presented here indicates that the effect is great enough to be important in attempts to perform precise quantitative determination on
B
ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
183R
GAS CHROMATOGRAPHY
OTC's. The use of an internal standard greatly improves the precision of the analysis and is mandatory for precise quantitative work. Since the calibration curves are quite linear, having the standard and sample concentrations closely matched is not of critical importance, although it remains a good analytical practice. This method is useful for analyses of coal liquefaction products. Kong et al. (23H) used fusedsilica OTC's coated with SE-52, polar Superox 20M, and liquid-crystal stationary phases and their mixtures were evaluated for the separation of isomeric sulfur containing PAHs containing three to five rings. Although columns resolve all three-ring isomers, no single column could resolve all of the four-ring or five-ring isomers. The optimum conditions for the GC separation of methyl esters of resin acid of um rosin using a OTC 50 m X 0.3 mm i.d. coted with a t1:l) mixture of poly(ethy1ene glycol) succinate and poly(diethy1ene glycol) succinate were found. Conditions were as follows: column temperature, 177 "C; carrier gas, nitrogen at flow rate of 0.5 mL/min. The analysis time was 25 min (27H). The retention indices of six isomers of trinitrotoluene were determined and complete separation of six isomers was obtained on the (75:25) mixture of OV-25 OV-210 ( I I H ) . A study was carried out by Onuska et al. (30 to identify and to determine organics in sediments from the western basin of Lake Ontario, particularly in the fine-grained sediments near the mouth of the Niagara River. The identification of organic compounds in the base/neutral sediment extract was carried out by WCOT-GC and HRGC/MS techniques using a 30 m X 0.31 mm i.d. OV-1 WCOT fused-silica column. The major classes of investigated contaminants were aromatics, PAHs, alkylated PAHs, phthlates, methyl esters of fatty acids, olefins, aldehydes, chlorobenzenes, and benzoates. In addition, all sediments were analyzed for 2,3,7,8-tetrachlorodibenzo-p-dioxins. Evans et al. (9H)studied the effect of on-column oxidation on the efficiency of apolar stationary phases. With an unsaturated hydrocarbon phase and air as carrier gas, dramatic changes of column efficiency were observed. Evidence is presented that suggests that this deterioration is due to the oxidative cross-linkin of the stationary-phase molecules. Ahnoff et al. (2H) stulied the catalytically induced decomposition of perfluoroacetylated aminoalcohols on glass and fused-silica OTC's. A test procedure was proposed, which allows the catalytic activity of a column against the analyte to be measured as the decomposition rate of the analyte. By measuring rate constants at different temperatures, the activation energy of the reaction was determined. By measuring decomposition rates of different compounds a relation was found between decomposition and chemical structure of the anal@. There was an acceptable separation and identification of the structure of perhydroanthracene, perhydrophenanthrene, perhydrofluorene, perhydroacenapthene, perhydrophenalene, cyclopentanodecalin, and fluorene on capillary columns packed with graphitzed thermal carbon black at 250 "C (%H).Thermodynamic characteristics of adsorption and retention indices on SE-30were measured. The effect of treating glass surface with KF and trisodium phosphate on the retention of polar and nonpolar compounds was investigated (13H). Alkanes, benzene, toluene, nitrobenzene, pyridine and polar derivatives of octane with such functional groups as NHz, OH, SH, Br, and CO were analyzed by using PEG 40M, PEG-40M + KF, and PEG-40M + Na3P04coated OTC's. The energy contributions of functional groups to partial molar free energy of sorption was calculated. Laster et al. (25H) described a technique for the measurement of photochemical processes within an OTC. A source of visible light placed inside the oven of a GC apparatus causes photochemical reactions to occur within the column. Such reactions affect the chromatographic behavior of substances eluting through the column. The observed reactions depend on the chemical properties of both the eluting sample substance and the stationary phase; e.g., various aniline derivatives react photochemically when absorbed on an alizarin stationary phase. The technique is sensitive to surface-catalyzed photochemical processes at very low concentrations. Martin et al. (26H)carried out gas chromatographic separations in a flat rectangular channel. The efficiency was controlled by the small dimension of the cross section. The amount of sample which can be injected depends on the large dimension of the cross section. The side-wall contribution to peak broadening was significant.
4
184R 0 ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
DETECTORS General. Reviews on ionization detectors (21-40, ultrasensitive detectors (50, and selective detectors (SI)for GLC analysis have been published. One particular review of common GC detectors stresses their limitations (In. It is clear from the number of applications reported that flame photometric (FPD), thermionic emission (TED), and photoionization (PID) detectors are taking their place as routine techniques alongside of the more traditional thermal conductivity (TCD), flame ionization (FID), and electron-capture (ECD) detectors. This is due to an increasing emphasis on selectivity in GLC analysis, and this trend is expected to continue for the immediate future. Multidetedor techniques are also being employed for selective detection allowing for a more positive identification of compounds by their retention times combined with peak response ratios obtained using different detectors. Fourier-transform infrared (FTIR) spectroscopy is continuing to be a strong area of investigation as a GLC detector and is especially useful when combined with mass spectrometer data. Thermal Conductivity Detectors (TCD). Few developments have been reported in the design of TCD detectors in the past 2 years. One paper has presented a numerical model of all significant heat loss terms ( 2 4 . Sensitivity for the constant current, voltage, and mean temperature modes of operation were shown to be equivalent at low sample concentrations. The constant temperature mode had a 7-10 times higher sensitivity but the S:N was no better. Increased heat loss due to conduction through the ends of the filament at high sample concentrations improves the linear response in the constant current and voltage mode. A second study described a new dynamic current drive method of powering the TCD that makes the current a weak positive function of the change in filament resistance (14.This allows improved linear response of the TCD from ppm levels to 100% concentration in the TCD cell cavity. Flame Ionization Detectors (FID). A review has been published concerning the origin of the FID on occasion of the 25th year since its invention (9K).New patent applications continue to be made for this detector. One describes the addition of a series of networks of electrodes, two pulse generators, and a second measuring amplifier to the conventional design, to obtain qualitative information of the substances being detected ( I I K ) . Another application claims increased dynamic range by splitting the gas entering the flame so that the GC effluent is injected by two or more nozzles, with an electrode placed opposite each nozzle (5K). Each electrode differs in capture surface area. In a modification to this basic design, the appropriate captive electrode is selected according to the sample concentration ( S K ) . Investigations concerning optimization of FID response continue to be reported ( I K , 7K, 12K). One of these studies showed that the FID linear dynamic range can be optimized by operating at higher H2 flow than required for optimum sensitivity ( I K ) . The design features of an FID in which Hz was replaced by CO as the fuel gas have been reported (2K). Substitution of CO for Hz did not result in deterioriation of the main characteristics of the FID (13K). Sensitivity was maximum when CO was used as both the carrier and flame fuel. Use of a negative collector potential instead of a positive one resulted in twice the detector sensitivty. Several studies concerning the flame chemistry of the FID have been reported. By use of a mass spectrometer, the previously unreported ions CllH9+and CI3H9+were detected in an FID type flame with CeHs additive (4K). Addition of NH3to the C6H6sample suppressed hydrocarbon peaks of m / z 100 but generated new peaks of m z 80 and 94. In another investigation, NH4+ions and their ydrates were detected in the cool drift space of an FID (8K), although previous work has shown that NH4+disappears in the burnt gases. It was postulated by computer simulation that H30+ions and NH3 ions from the burnt gas will undergo proton transfer in the cool drift space at NH3 concentrations of about 1 ppm. Computer simulation was also used in another study concerning reactions in the FID detector (IOK). The CH4yield and ionic yield were the same for decomposition reactions when H, was used as fuel and also when CO was used. Basic theory of electrical conduction in the FID and experimental results on the analysis of ions in the detector have been reviewed ( 3 K ) . Electron Capture Detector (ECD). The design and
h
GAS CHROMATOGRAPHY
o eration of the ECD (15L)and application of the ECD to $COT gas chromatography (12L,I4L) have been reviewed. One review discusses the problems of detector calibration at low concentrations and use of the ECD as an ion-molecule reactor (14L). Several new designs or modifications of the ECD have been reported (2L,5L, 8L, 12L,18L, 20L).The most interesting development was a nonradioactive ECD which uses a thermionic emitter as the electron source (12L).This detector was sensitive to all common electron-capturing compounds tested. For certain substances, a S:N of 1W1at the 1-pglevel was attained, and a dynamic range of 6 orders. No temperature limit of operation exists for this detector, which has a new mode of operation due to the phenomenon of space charge amplication. In a design for a high-temperature dc ECD, the cell consisted of two chambers separated by a variable restriction (18L).By testing the response of this detector using lindane and aldrin, the authors confirmed that cation-anion neutralization is not a necessary condition for observing electron-captureresponse. The configuration also circumvents contamination of the radioactive foil from the column effluent. A laser-modulated ECD has been reported which combines the sensitivity of ECD with the selectivity of absorption spectrometry (SI,).Three distinct response mechanisms were discussed direct vibrational excitation, bulk gas heating, and photodetachment. To prevent the contamination of the radioactive foil in an ECD, one new design included a flash ionization gas feed system (2015).Base-line drift from temperature program operation was corrected in another system by the voltage used to drive the linear temperature programmer (2L). Since this voltage is inversely proportional to temperature, it was inverted and amplified to cancel out the rising background usually observed with temperature program operation. For WCOT column GC analysis, a micro-ECD with 130-pL cell volume was developed (5L).This was accomplished by using a high-frequency ceramic tube as insulating material. The ECD can be operated a t high temperatures. Other studies have been reported concerning the mechanisms of response of the ECD. In one investigation, evidence for two distinct response modes in pulse-driven ECD was presented (IL). One was a classical neutralization process and the other a recently proposed space-charge mechanism, for which the emphasis is placed on transport processes rather than chemical reactions. A separate study on the effects of applied fields on positive ions in pulsed ECD reaffirmed the validity of the space-charge model (6L). Experiments to determine the ECD response to a series of halogenated methanes showed that the classical dissociative electroncapture mechanism alone could not account for the results obtained (1115).The ECD mechanism with respect to different amounts of oxygen and water in the Nz carrier gas was discussed in another investigation ( I 7L). Maximum sensitivity was obtained with 6 mg of HzO per 1L of carrier gas and the concentrations of HzOand Oz corresponded to their ratio in the complex (H20)302-.Future investigations concerning the ECD mechanism may be aided by a special 63Niionization cell in which ion densities can be measured (IOL). This method can calculate ionization parameters of any 63Nior Pt cell. Several studies concerning the effect of experimental parameters on ECD response have appeared in the past 2 years. A theoretical analysis of the space-charge effect on ECD response has been reported (16L).The dependence of saturation current on various experimental parameters was determined for 3H, 63Ni,and 24Amsources. Another study investigated the effect of pulse frequency on ECD response (19L).When pulses of 100-ps period were used, the detector acted as a concentration-sensitive detector for BHC and p,p'-DDE, but as a mass-sensitive detector for p,p'-DDT. With 2000-ps period pulses, the ECD behaved as a mass-sensitive detector for all of these substances. The effect of different ECD cell designs with respect to peak shape has also been investigated (21L).Measured peak shapes were compared to those generated by computer simulation. One conclusion was that for WCOT operation, the ECD does not require any abnormally high purge flow. Further work has been reported on the sensitization of ECD response. The use of oxygen-sensitized ECD for analyte identification of polycyclic aromatic amines and hydroxide was examined for compounds in which an EC-enhancing
chemical tag was attached to the amino group or the methylation of the hydroxy group (4L).In many cases, when response enhancement is dependent upon structural differences of the unresolved components and the sensitized responses are linearly related to the concentration of each analyte, the method can be successfully applied. Detection of CO can be sensitized by adding NzO to Nz carrier gas (9L). This increased response for CO is explained by the catalytic conversion of CO to COz in the presence of HzO on the hot detector walls. This effect is stable and reproducible. In a second study of Nz doping, differences between some isomers were great enough for this technique to be used for identification (22L).For example, a 20-fold difference was observed between benzo[a]pyrene and benzo[e]pyrene. In other studies of interest, the response of aromatic hydrocarbons to ECD were predicted on the basis of known ionization potentials (23L).A novel calibration marker scheme was reported which simultaneouslyprovides a retention index scale and intefnal calibration curve (13L). This was accomplished by using normal bromoalkane, with each compound present at stepwise increasing concentrations. Working with a standard ECD, the detection limit of some strong electrophores was determined to be in the attogram range (7L). The detection limit of N,N-dipentafluorobenzoylpentafluoroaniline was 90 ag with S:N = 2.1. Flame Photometric Detectors (FPD). These have been used as routine detectors in many studies in the past 2 years, and the list of their applications has rapidly expanded. A new double-burner design has been reported with a lower and upper burner arrangement (5M). The lower burner is located with the positive electrode supply, and the upper burner with the ne ative supply. Selectivity and sensitivity of the FPD towarcf N, P, and S compounds was increased by adding a transparent quartz sleeve around the upper burner. The standard FPD has been adapted to the gas-phase detection of fluorescent compounds (6M). Fiber optics and a monochromator were used to avoid lengthy transfer lines. This configuration is useful for the subnanogram detection of polycyclic aromatic compounds. A new model of FPD response was reported and applied to FPD signal evaluation (4M).The detection mechanism was quantitatively described by a second-order polynomial fit. By adjusting FPD parameters, selectivity for other elements than S or P can be obtained. This was demonstrated in one study where an FPD was used to detect volatile and nonvolatile organotin compounds in aqueous media (3M).Other studies regarding detector optimization have been reported. A commercial FPD was tested in one investigation and while response in the S-mode depended on Nz flow to the detector, this variable showed little effect in the P-mode ( I M ) . Response was linearized and the detection limit improved by use of permeation tubes. Effect of FPD temperature on response for the S and P modes has also been reported (2M).The peak heights in S-mode decreased with increasing detector temperature, while the peak heights in the P-mode were larger. The P/S response ratio increased by a factor of 6 from detector temperatures 80-160 "C. At constant temperature, selectivity varied with the air flow by about 2 orders. Photoionization Detectors (PID). As was stated for the FPD, the PID is in routine use, and a number of applications of this detedor have appeared since the previous Fundamental Review. Little work, however, has been performed specifically to improve the technique or study the fundamental operation of the PID. One interesting design combined a PID and PID-based ECD (3N). In the ECD mode, the detector used a readily photoionizable dopant gas, ionized by UV lamps, to give the electron base-line current. Characteristics and performance of this detector were comparable to those of ECD, with a linear response from pico- to micrograms. Factors involved in the PID response were studied in another investigation (2N).As expected, ionization potential was the most important factor; however, the relative number of a-electrons was not a significant additional factor. One study reported the use of a PID run sequentially with 9.5, 10.2, or 11.7 eV lamps to classify hydrocarbon types at nanogram levels in complex mixtures ( I N ) . Classification of hydrocarbons was performed depending upon the response ratios of peaks detected using the various lamps. Use of PID compared to FID and infrared for the characterization of aromatics in complex mixtures was reported (4N).Enhanced PID response at 10.2 ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
185R
GAS CHROMATOGRAPHY
eV compared to FID was observed, but the aromatic/aliphatic selectivity of the PID did not allow low detection limits for aromatics in complex aliphatic mixtures. Better selectivity for polyalkylated aromatics, naphthalene, and N-heteroatoms was obtained with 9.5- and 8.3-eV lamps, but the sensitivity of these lamps has much less than the sensitivity of the 10.2-eV lamp. Thermionic Ionization Detectors (TID). Applications involving the TID continue to increase. One patent application has described a flexible TID design that allows the operator to change the electrical connections to the electrodes and the position of the excitation electrode with respect to the flame and collector (40). With the design, chromatograms of unknowns can be obtained using different detector configurations to develop qualitative data which is useful to indicate specific types of compounds. Another detector design is based on a unique ceramic core thermionic source with a surface coating of alkali ceramic activating material (30). This surface coating determines the response characteristics of the TID; a low Cs coating in a H2/air environment gives high sensitivity and specific response to compounds containing N and P, while a higher Cs concentration in an N2 environment gives high specificity to compounds containing electronegative functional groups such as nitro groups. Other studies investigated the characteristics of thermionic detectors. Measurements of gain and noise using Rb and K vapor have been used to develop an approximate theory for space-charge limited operation (50). Sensitivity for inorganic phosphorus compounds was found to be 2-4 orders of magnitude larger than chlorides of other elements (20). Detectors with indirect heating were found to be more stable than conventional detectors. Relative sensitivities for a wide variety of nitrogen-containing organics have been reported (10,60). Infrared (IR) and Fourier Transform Infrared (FTIR) Detectors. Much work was reported on the characteristics and development of GC-FTIR in the past 2 years. The number of recent reviews on this technique is a testament to its growing importance (4P,SP, 1l P , 12P, 15P, 19P, 20P, 26P). The potential of GC-FTIR when combined with GC-MS data for compound identification is great, and one reviewer has predicted that a commercial GC-FTIR-MS will soon be available (4P). Larger FTIR data bases for compound search, improved performance at trace concentrations, and better quantification are areas of GC-FTIR which still require considerable development. Most developments reported since the 1980 Fundamental Review have dealt with the software and operating characteristics of GC-FTIR. In one study a low-volume short light pipe cell was developed as a WCOT/GC-FTIR interface (18P). Chromatographic integrity was preserved in this system and detection limits of 20 ng were obtained. Direct inlet to the cell can be accomplished by using fused-silica WCOT columns. The routine operational level of 100 ng, however, precludes the use of this system for routine trace analysis. Another system has been reported to achieve low nanogram detection limits (22P). This system uses narrow-bore WCOT columns, while the previous system was better suited for wide-bore columns. A library search system was used to identify compounds from the analysis of a petroleum distillation fraction and the pyrolysis products of a polymer sample. An interface for GC to a commercial FTIR instrument was described in one study in which a mass spectrometer was then coupled in series (21P). Capabilities of this system were demonstrated by using packed-column GC and a standard mixture. Reconstructed chromatograms were obtained from MS total ion plots. Mass spectrometry has been shown to be a complementary technique to GC-FTIR in other investigations (5P,16P, 24P). The chief difficulties of GC-FTIR arise from the need to achieve better sensitivity and to develop larger data bases (24P).GC-FTIR was found to be a powerful tool for aromatic isomer differentiation in complex waste extracts, as even poorly separated GC components were identified (5P). Approaches to qualitative and quantitative data evaluation for GC-IR-MS analysis have been presented (25P). Descriptions of the design and operation of GC-FTIR instruments (2P,9P) and application of GC-FTIR to toxic substances in environmental samples (6P) and pesticide chemistry (1OP) have been presented. FTIR is especially valuable for isomer identification (2P).If components are not 188R
ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
resolved by GC, then IR spectra for each unresolved component may be generated by spectral subtraction (lop).The minimum detection limits of 55 toxic substances by packedcolumn GC-FTIR have been reported, with the greatest sensitivity for aliphatics and aromatics containing oxygenated functional groups, and the poorest sensitivity for alkyl halides and aromatic hydrocarbons ( l o p ) . Sensitivity was inversely proportional to the light pipe temperature. Sensitivity was improved in another investigation by factor analysis, compared to present real-time reconstruction procedures (17P). Reduction in computation time was also obtained. Sensitivity of one FTIR detector tested was considerably less than that by a conventional nonselective GC detector (14P). A very poor linear range was also observed for FTIR detection. Advantages and disadvantages of inserting a PID in line with the FTIR was discussed. Improvements in quantitative GC-FTIR require software as well as instrumental development. In one study, the GC trace was constructed directly from raw interferometric data (23P). Theoretical considerations were presented to show that quantitative data can then be directly obtained. A complete qualitative and quantitative analysis of a GC-FTIR experiment without computing a single Fourier transform may be possible. Other mathematical techniques to improve GC-FTIR analysis include a cross-correlationS/N enhancement (13P). Some problems were encountered with peaks containing substantial amounts of low-frequency noise. Novel developments in GC-FTIR include the use of deuterated retention markers for the calculation of accurate retention index values from a single experiment (7P) and the use of low-temperature matrix isolation FTIR as an alternative to on-line gas-phase GC-FTIR (3P). One study using conventional IR showed that effective results can be obtained by a GC effluent splitter and a system which allows eluting components to be trapped in adsorption tubes for later IR analysis or by passing components directly to the IR cell through a heated transfer line where they are trapped by a bypass valve UP). Alternatively, the IR cell can act as a functional group detector for on-the-fly analysis. Spectrometric Detectors. Many more applications of atomic spectroscopyof GC peak detection have been published since the previous Fundamental Reviews. As highly sensitive detectors with tunable selectivity, these detectors offer much to the analysis of both organics and inorganics. Several reviews of atomic spectrometric detectors have appeared (124,134, 23Q-25&,284, 29Q). Many of these reviews deal primarily with microwave and inductively coupled plasma emission spectroscopy (124,234,244,28&). One review of GC-atomic absorption detection has been published (254). The atmospheric pressure microwave-induced plasma (MIP) was the most popular spectrochemical detector studied. Design and optimization of a He-MIP has been described (5P, 64,204). One study reported detection limits of 3-20 pg for Fe, P, Br, and C1 but 1400 pg for S (54). The S/N can be enhanced by data smoothing for a rapid-scanning spectrometer (204). Use of an original device to generate the He plasma has been reported (64). Detection limits, dynamic ranges, and selectivities for H, C, F, C1, Br, I, and S were determined in one study, but these parameters for N and 0 could not be measured because of interference from air through leakages of the tubing and valve system (274). Use of the He-MIP techniques for low molecular weight sulfur-containing compounds was found to be specific enough that coeluting compounds not containing sulfur did not interfere with the analysis (144). The small quartz plasma tube of the MIP was easily interfaced with the GC column. By simultaneously measuring C, H, D, N, P, 0, S, F, C1, Br, and I in GC effluent by MIP, it is possible to identify compounds from the various elemental ratios (264). A dual WCOT column system allowed parallel detection using MIP and FID or ECD (164). In an MIP system using a polychromator, a refractor plate was mounted on a stepper motor to give dynamically background-corrected data points (11&). Four emission wavelengths were simultaneously monitored to produce multichannel chromatograms. For WCOT columns, the data acquisition rate of 1-3 points/s must be improved. Developments in GC-atomic spectroscopic methods other than MIP have been reported. A sequential-scanning slew monochromator was developed for an inductively coupled plasma (ICP) as a GC detector ( l O Q ) . Multielement monitoring using a single-channel spectrometric detector can be
GAS CHROMATOGRAPHY
performed providing there was sufficient time between GC peaks, The low- ower Ar/Ar and high-power N/Ar ICP techniques have ieen compared (21Q). Advantages of the N-cooled plasma include increased sensitivity by using higher power input. Some developments in atomic absorption (AA)-GC have been reported. The interfacing of an AA spectrophotometer to a fused-silica WCOT column for detection of organomecury(I1) compounds has been described (8Q). A quartz capillary transfer tube was used and ita length minimized by placing the AA unit on top of the GC. Another investigation has presented four novel atomization cells for the determination of volatile organometalliccompounds ( 9 8 ) . A statistical procedure was used in the o timization of the cells. In the most sensitive design, the 8 C effluent was fed to a small hydrogen diffusion flame, and the atoms from this flame were swept into a flame-heated ceramic tube. Novel chemiluminescenedetectors have been developed and applied to the determination of volatile polyhalogenated hydrocarbons (30Q) and atmospheric ammonia and amines ( 1 8 6 ) . The former was based on the chemiluminescene reaction with atomic sodium vapour under reduced pressure and it compared favorably with an ECD in sensitivity and was better with regard to linear dynamic range and selectivity. The other detector used a commercial chemiluminescent NO, analyzer with formation of NO from nitrogen-containing compounds by pyrolysis on a hot Pt catalyst. Use of GC to ensure quantitative capability in rotationally cooled, laser-induced fluorescence (RC-RIF) has been reported (17Q). Very high selectivity is provided by RC-RIF, and detection limits are in the picogram range. A He-Ne laser operatin simultaneously at 3.39 pm (IR) and 0.63 mm (vis) was usefas a selective detector for hydrocarbons in GC effluent (22Q). Detection limits were better than the best achieved with TCD, and the detector does not respond to H20 or COz. Studies of the characteristics of a GC-laser optoacoustic spectrometer have also been reported (31Q). A review on the use of lasers for chromatography state that their use can result in gains in selectivity and sensitivity (15Q). Little attention for GC use of lasers is a result of the high resolving power of GC which makes selective GC detection less important than for other techniques such as liquid chromatography. Other spectrometric techniques used for GC detection include ion mobility spectrometry (1&-3Q),far UV absorbance (4Q), matrix isolation fluorescence (7Q), and metastable transfer emission (198). The ion mobility spectrometer in the negative mode is similar to ECD, and enhanced response to low molecular weight halogenated compounds was observed when doped with O2 (18).At O2concentrations of 0.5%, the minimum detectable amount of CC14was 600 fg. The tunable selective capabilities of this detector were increased by using a photoionization source instead of 63Ni (2Q). Other improvements such as a modified cell design and changes in operating conditions to optimize applications of ion mobility spectrometry to GC detection have been described (3Q). A far UV absorbance detector with three lines sources at 120, 129.5, and 147 nm has recently been described (4Q). Since most compounds absorb at these wavelengths and very stable UV lamps are available, this detector may prove to be very useful for specific GC applications. Matrix isolation fluorescence was accomplished by depositing GC eluents on a movable surface in the head of a closed-cycle cryostate ( 7 8 ) . The GC carrier provided the matrix. Accurate quantification of pyrene from a complex NBS reference standard was demonstrated even though chromatographic separation of pyrene from other fluorescent sample constituents was not achieved. Ionization Detectors. Modifications in the operation of a hydrogen atmosphere flame ionization detector (HAFID) to increase its selectivity to phosphoroush (2R) and siliconcontaining compounds (3R)have been described. By doping the HAFID with vapors of ametal-containing compound, in excess of that required to obtain positive responses of Sicontaining substances, an ionization quenching phenomenon was observed which produced ne ative chromatographicpeaks (3R). A modified FID was used to obtain selective analysis of oxygen-containing compounds (7R). Two microreactors were positioned between the column and FID. Selectivity of this detector to oxygenated compounds was 107:1over hydrocarbons. The FID has been compared to an active nitrogen
afterglow detector and was found to have better detection ability and linear dynamic range (5R). The N-afterglow detector, however, has superior selectivity and potential ds a metal-specificmultielement detector. Good limits of detection for the N-afterglow detector were obtained for the analysis of organomercurycompounds in environmental samples (6R). Other detectors operated by means of a point discharge in dry Ar (1R) and by dual-flame ionization (8R). A hydrocarbonsensitized argon ionization detector for the detection of inorganic compounds has been described (4R). Electrochemical Detectors. Little new development of these type of detectors for GLC analysis has been reported in the past 2 years. The operation and applications of the Hall 700A electrical conductivity detector have been reviewed ( 2 s ) . Performance of this detector as a sulfur-selectivedetector has been studied (IS). Lower detection limits for S-compounds were obtained for the Hall 700A than for an FPD operated in the S-mode. Electrical conductivity detection was found to be a highly sensitive technique in GC when steam is used as the mobile phase ( 3 s ) . A catalytic oxygen-type detector was described for the quantitative determination of hydrogen isotope mixtures (45"). Mass Spectrometry Detectors (MS). In addition to having a very high sensitivity, mass spectrometerscan function as universal detectors or tunable specific detectors. Unless cost is the determining factor in GC analysis, the mass spectrometer is usually the detector of choice. Many applications of MS to GC analysis have appeared in the past 2 years; however, little development of the technique has occurred in this time period. A GC-MS with a low-pressure microwave-induced plasma (MID) has been developed for selective elemental detection (2T). The MIP converts organic molecules into a few simple neutral species which are detected by MS. Elements present in the original molecules determine which species will be formed. The system can be used for selective element detection and elemental ratio determination. Another development of interest is a WCOT column GCFourier-transform mass spectrometer (GC-FTMS) (427. High-resolutionmass analysis is possible with WCOT columns. An important feature of this system is that it can switch peaks at high resolution over an arbitrarily high mass range. An important development for chromatographers is the introduction of MS instruments by instrument companies that are designed specifically as GC detectors (4Q, 1 T , 35"). The mass selective detector by Hewlett-Packard (IT,35") is a scaled-down quadrupole MS that retains the operating modes (full scan of mass spectrum and selected ion monitoring) of larger instruments, but at a significantly lower cost. The other development is the ion-trap detector from Finnigan Corp. ( 4 8 ) . It is a unique detector that uses radio-frequency fields to store ions. Detection of ions is by an electron multiplier. The same type of data can be obtained from the ion trap as from a conventional quadrupole MS. Both of these detectors will reduce the cost of MS detection to a level that is within reach of many laboratories that previously could not consider GCMS detection. Combination Detectors. As a means of achieving increased ability of identification of GC peaks, several dualdetector designs have been reported. In some cases, the second detector was added to improve quantification. This new section was added to the Fundamental Reviews this year to address an increasing interest in dual-detector design. The GC-MS/FTIR combination has already been mentioned (21P). Other evaluations of this combination have been presented ( I U , 3U). Because of the large amount of data generated by these techniques, for both qualitative and quantitative analysis, future developments should soon lead to powerful commercially available system. As has so often occurred for the GC-MS combination, however, it appears as though the necessary software and data-base development is lagging far behind the instrumental development. A tandom FID/PID system was used to differentiate between aliphatic and aromatic hydrocarbons after GC separation ( 1 7 0 . The PID in this arrangement must be gas-tight and have a low cell volume. This same arrangement was used to classify hydrocarbons according to their degree of saturation (IOU). Effects of varying the operation parameters of a PID and PID/FID splitter to PID/FID response ratios have been reported (2U). Averaged normalized response ratios have been reported (2U). Averaged normalized response ratios can be ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
187R
GAS CHROMATOGRAPHY
used to estimate chemical classes of organic compounds in ambient air. FID combined with NPD has also been reported and NPD/FID response ratios for permethylated cytokinins were determined (15U). Response ratios for other detector combinations have been reported. These include ECD/PID ratios for organic nitro compounds (7U), NPD PID ratios for the identification of amines (ISU), and NP /Hall 700A electrical conductivity detector response ratios to confirm identities of chloroanilines and chloronitroanilines in complex samples (8U). The advantages of using a PID with FTIR detection have been described (9U). A PID can be used for the quantitative evaluation of chromatograms from FTIR analysis. A new line of detector heads with the ionization cells ECD and NPD in series has been developed for the simultaneous GC identification of chlorinated hydrocarbons, organophosphorus pesticides, and triazines (4U). Results for a PID and electrolytic conductivity detector in series for the determination of halocarbons and aromatic compounds in drinking water were comparable to those obtained from separate PID and electrolytic conductivity analysis (6U). Construction of a polyimide effluent splitter for multiple detectors in WCOT-GC has been described (13U). Multiple detection systems combining more than two detectors have been developed. PID-ECD-FID in series were used to determine low molecular weight trace components of nonurban atmospheres (12U). The separation efficiency of the system was not degraded by this combination, but unstable compounds may decompose in the ionization chambers of the PID or ECD. Two different groups have used combined FID-ECD-FPD systems (5U, 11U). In one, the FID is in parallel to a series ECD-FPD (5U). Determination of acrylonitrile in olive oil was demonstrated. The second ECD-FID-FPD combination was used to determine hydrocarbons containing different functional groups ( I 1U). Another simultaneous multidetector system was applied to sulfur and nitrogen mustard compounds (14U). With up to four detectors, including FPD in N or S mode, FID, dc-ECD, and the model 700 Hall electrolytic conductivity detector, it was possible to quantify components which elute very close together.
A
OTHER TECHNIQUES Physical-Analytical Measurements. The use of gas chromatography to perform various physicochemical measurements is well established. Providing the accuracy of the determination is great enough, GC is often the technique of choice for such studies, because of the simplicity and speed with which an experiment can generally be performed. One review has appeared which discussed the use of GC to measure thermodynamic properties of solution (28V). Another review described methods for calculation of activity coefficients of volatile compounds at infinite dilution using GC (13V). This area has continued to receive considerable attention since the previous Fundamental Review. Activities of water in CaClzsolution were measured by the flow method and were close to values previously reported (37V). Activity coefficients at infinite dilution of paraffins, olefins, aromatic hydrocarbons, and chloroparaffins in 12 stationary phases at 30-80 OC were reported (4V). Similar measurements for acetates, alcohols, nitriles, nitromethane, chloroform, and carbon tetrachloride have appeared (6V). Effects of the nature of palmitic, pimelic, sebacic, and lactic acid stationary phases on activities of 38 solutes were determined (5V). These data for industrially important compounds were reported (36V). The 35 solutes in 34 different solvents covered a wide range of polarity, polarizability, and degree of association. Investigations of the relationship between activity coefficient data with respect to molecular structure of solutes have been performed (22V, 9V). An analysis of literature data showed good correlation between bulk and surface activity coefficients with molecular interactions in the surface layer playing a role similar to that in the bulk phase (9V). New GC methods for determining various physical properties have been reported. Applications of these methods were for determining tie lines from ternary liquid-liquid equilibriums (33V), nonpolar solubility parameters of organic solvents (25V), adsorption equilibrium constants (ZOV), diffusion coefficients of hydrogen atoms in gases (27V), and pressures of saturated vapors and heats of evaporation of organic com188 R
ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
pounds (12V). Direct GC determination of the solubility of light gases in liquids has been performed (26V). Henry’s law constants for 11gases in three hi h molecular weight n-alkane solvents were reported. Other fat, for the surface and bulk activity coefficients in nonelectrolyte mixtures (IOV),partition coefficients of inert solutes on self-associatingbinary solvent mixtures (1V), atom vapor diffusion coefficients by hightemperature GC-AA (32V), and diffusion coefficients of some derivatives in dinonal phthalate (7V), have been determined by GC. The GC data usually were obtained with good precision (a few percent) and generally agreed favorably with data from other techniques. Investigation of thermodynamic properties has continued to be a popular application of GC data since the previous Fundamental Review. There does not seem to be a general direction for this work, however; this may be a result of the flexibility of the GC approach which is suitable for many different applications. In a study of Flory-Huggins interaction parameters for the mixing of water and PrOH in poly(ethy1ene oxide), the existence of a highly structured complex in concentration solution was confirmed (11V). Thermodynamic solution parameters were calculated for acetophenones in various stationary phases (16V),isomeric polycyclic aromatic hydrocarbons in nemantic liquid crystal (18V),and six-carbon acetylenic compounds in alkanes and ether solvents (30V). Other studies included the determination of thermodynamic characteristics of hydrocarbon adsorption on tungsten sulfide (14V),the solution thermodynamics of hydroxylic derivatives and related compounds (24V), thermodynamic properties of weak hydrogen bonds in solutions (8V),and the derivation of relations to convert different forms of the distribution coefficients into thermodynamic distribution coefficients (31V). Contributions of different structural elements to the thermodynamics of sorption were investigated (35V). GC application to various kinetics experiments has been reported. One author has suggested the application of reversed-flow GC to the study of the drying step in the preparation of supported catalysts (21V). Kinetic parameters including rate constants, activation energies and frequency factors can be obtained. GC provided more reliable kinetic data than other techniques in the investigation of monomer-reactivity ratios under high-pressure conditions (34V). An interesting safety feature of the GC method was that it could be remote controlled. Miscellaneous uses of GL for physical-analytical measurements include the determination of phase transitions in polymers (23V), determination of potential barriers and equilibrium angles of internal rotation for methyl derivatives of biphenyl and terphenyls (15V), study of the effect of molecular structure on values like molar heats of evaporation (2V), and the chemical-physical properties of binding polymers (3V). The theoretical basis for determination of second virial coefficients by GC has been presented (17V). Studies of the theoretical and practical uses of GC to determine liquid-liquid partition data (38V), the determination of molecular polarity by retention data obtained on two phases (19V), and the effect of liquid-surface adsorption on GC determination of enthalpies of solution (29V) have also appeared. Inorganic GC. Less work has been reported in this area since the previous Fundamental Review; however, the importance of GC in inorganic chemistry has not diminished. Applications include the determination of metal species, investigations on the complexation of metals by various ligands, kinetics of reactions, and surface and catalysis studies. Some studies that could have appeared here are referenced in the “Novel Applications” section. Since many inorganic GC studies can now be classified as routine, some selectivity in the reported work was applied to choose the references most representative of the inorganic-GC research performed since the previous Fundamental Review. In spite of the continuous application of GC to inorganic chemistry over many years, there are suprisingly few books and general reviews on this subject. One book has been published since the previous Fundamental Reviews which covers a large amount of work performed using GC for organometallic compounds (5W). There is still need of more such work for the field of inorganic GC. Several reviews have also appeared in the past 2 years. These include the thermal characteristics and GC of metal chelates (14W),use of GC in
GAS CHROMATOGRAPHY
the determination of metals (19W) and heavy metals (2W), and use of GC in catalysis (27W). The use of GC-MS in heterogeneous catalysis and adsorption studies has been discussed (13W). Separation and detection of trace elements by volatilization followed by GC has also been reviewed (1W). Analytical methods for inorganics and organometallics have been reported. Chromium was determined as its acetylacetone, trifluoroacetylacetone, and hexafluoroacetylacetone chelates (3W). Sensitive detection was obtained with no interferences from the free organic reagents by using a nitrogen phosphorous flame ionization detector. Determinations of n, Cd, Cu, Ni, Pb, Hg, and Co as their diethyldithiocarbamates have been made using both FID and mass spectrometry detectors (1OW). Trialkyllead halides were speciated by GC-FID with detection limits as low as 5 ng (6"). S ecific element detection for WCOT fused-silica column G 8 analysis of Ge, Sn, and P b tetraalkyl compounds was accomplished by microwave-induced He plamsa spectroscopy (8W). Representative redistribution reactions in gasolines were monitored. Other analytical studies include the determination of Cu, Ni, and Va in biological samples using a fluorinated Schiff base with detection limits of about 5 pg (20W), elemental analysis by using di(trifluoroethy1)dithiocarbamate chelates (9W, 18W) and GC characteristics of tributyltin(1V) N,N-dialkyl dithiocarbamates ( 4 W ) . A series of papers studying the use of porphyrin complexes have also appeared (15W-1 7W). The prophyrin ligand can complex a wide variety of metal species and thus could occupy a unique position in metal chelate GC (16W). Studies of prophyrin complexes have included transition-metal complexes with Kovats Retention Indices from 5200 to 5600 (16W),metal(II1) and metal(1V) complexes as the trimethylsilocy derivatives ( I 7W), and silicon(1V) derivatives of prophyrins with polar substituents (15W). The chromatographic properties of a variety of organometallic species have been studied. For a series of metal /3-diketonates, a linear relation was found between the logarithm of the retention volume and carbon number of the central alkyl group or that of the terminal group in the ligands (12W). Of the 25 possible products of synthesized mixed ligand Cr(II1) complexes in another investigation, 24 were resolved by a fused-silica WCOT column (22W). Manganese(II)-bis(3-heptafluorobutyryl-IR-camphorate) was found to be an effective agent for the GC resolution of racemic cyclic ethers (21"). GC separation of lanthanide chlorides and lanthanide chloride-aluminum chloride complexes has been studied by using a column packed with quartz granules (24W). GC techniques can be used for a wide variety of inorganic chemistry applications. Thermal stabilities of oxalate coordination compounds have been reported (26W), and the kinetics of their thermal composition (25W). Effects of ligand doping on the GC of trifluoroaeetylacetonates of chromium(111) and iron(II1) have been studied (23W). In this investigation trifluoroacetylacetone was added to the carrier gas. Properties of the surface of oxides of nickel(II), cobalt, and cadmium with regard to adsorbates possessing different electronic structures were also studied (7W). An increase in the heats of adsorption on the oxides of Co and Cd as compared with those on their hydroxides was noted. Applications of GC to surface analysis were illustrated by determination of the surface acidity of A1(OH)3 as well as qualitative and quantitative characterization of the catalytically active fraction of several oxide surfaces ( I I W ) . Novel Applications. Whether an application is classified as novel is, in part, a subjective decision. Every year there are several applications of GC to new compounds or new problems that only represent minor differences from wellstudied systems. In this section an attempt has been made to restrict coverage to ingenious applications that illustrate the wide range of possible uses of gas chromatography. One study used a chromatographic pulse method to determine the surface area of nickel catalyst ( 9 X ) . CO pulses were injected into the carrier gas stream which passed over the catalyst surface through one side of a bridge in a TCD cell. Adsorbed H2was displaced from the catalyst surface by CO in a single peak. Another investigation showed how the mutual diffusion coefficients of two gases A and B can be determined in an empty GC column ( 6 X ) . Component B entered at an intermediate position of the column as a continuous flow with the carrier gas. The other component is
d
injected into the closed end of the column, with the detector at the other end. By repetitive stopping and starting the flow of B, the diffusion of A into B can be determined from the peaks detected. Diffusion coefficients have also been determined with a similar system but by reversing the carrier gas flow at definite known times ( 5 X ) . This reversed-flow GC method can be used to study the rate constants of surfacecatalyzed reactions ( 4 X ) . Novel uses of a microreactor-GC method have been reported ( 3 X , 8x1.One system was a high-pressure microcatalytic pulse reaction system combined with a high-pressure GC ( 3 X ) . A reactant pulse was injected into the high-pressure He carrier and passed through a small catalyst bed. Because products were analyzed by GC in situ, activity measurements are rapid and consume a minimum of the reactant. In the other study, a hydrogenation microreaction was used together with GC-MS to identify the positions of double bonds in normal and branched alkenes (8X). The method required fiist to determine molecular weight and degree of unsaturation by bypassing the catalytic column, identification of the carbon skeleton by catalytic hydrogenation using hydrogen as carrier, and then identification of the double bond position by using deuterium as carrier. New GC techniques have been introduced. A back-flushing technique has been described in which a period of isothermal operation is followed by a program of longitudinal temperature gradient when gas flow is reversed ( I X ) . Retention times of poorly volatile solute were shorter and column temperature lower than for classical GC methods. Use of an increasing stationary temperature gradient along the length of a GC column has been proposed ( 2 X ) . The same advantages as obtained for temperature programming could be achieved without temperature transients. Reduced retention times, sharpening of peaks, and higher symmetry were predicted for such a system. The technique of vacuum GC has been suggested as a means of extending the molecular weight range of GC for analysis of high-boiling hydrocarbon mixtures ( 7 X ) . This method was characterized by nearly pressure-independent distribution coefficients, shift of optimum flow rates to higher values, and shorter analysis times but reduced separating power, compared to atmospheric pressure GC.
QUALITATIVE AND QUANTITATIVE ANALYSIS Qualitative Analysis. Correlation between Kovats retention indexes (AI) and molecular structure is a continuing interest for qualitative analysis. Saura Calixto et al. (35Y) reported that the Kovats retention index of 25 homologous series of esters, aldehydes, ketones, and alcohols increase with the increasing polarity of the compound and decrease with chain branching and the shift of functional group to the center of the chains. Macak and associates (27Y) measured the retention indexes of near 70 alkyl derivatives of benzene and naphthalene at two temperatures. They found that the steric factors and the steric position of the alkyl group on the molecules have a decisive effect on the elution order of isomers and on the retention indexes increment. The increase in the Kovats retention index was higher when the alkyl groups were in the ring than in a side-chain position. For a homologous series of halogen esters of C1-CI8 aliphatic alcohols on stationary phases of varying polarity, the retention increased with increase mass of the halogen atom and with increasing polarity of the stationary phases (24Y, 25Y). Correlation between polarity of liquid stationary phases and the retentions of solutes with varying number of methylene group was examined (34Y, 37Y). McReynolds constants for solutes of different methylene group were determined for 55 liquid stationary phases (34Y). Novak et al. (30Y) correlated the specific retention volumes of homologous compounds with temperature and methylene number. Good agreement between calculated and measured specific retention volumes for given methylene number and temperature were reported (30Y). A method based on polynomial interpolation for calculating linear programming temperature GC retention indexes was described (23Y). The determination of linear PTGC retefition indexes and the identification of phenols (42Y) and many environmental organic pollutants were given and discussed (22Y). The temperature effect on retention indexes of hydrocarbons on methylsilicones and squalene liquid stationary phases was discussed, and retention indexes of 43 hydrocarbons between ANALYTICAL CHEMISTRY, VOL. 56,
NO. 5, APRIL 1984
189R
GAS CHROMATOGRAPHY
40 and 70 "C on OV-101 liquid stationary phases were measured (21Y). Correlation between retention indexes and molecular structure and temperature allows the prediction of solute compounds retention characteristics with good accuracy (38Y). The difficulty, however, may arise due to the poor thermal stability of the stationary phases. Larson et al. (26Y) studied the effect of fused silica column environmental stress such as high column temperature and oxidation on retention index reproducibility. The on-column oxidation of nonpolar and polar silicons stationary phases was also evaluated by Evans (8Y) and found slight even at 225 "C column temperature. The methylphenylsilicones are more stable than polar phases such as (trifluoropropy1)methylsilicones and (cyanopropy1)methylphenylsilicones under high-temperature on-column oxidation. Gas chromatographic Kovats retention indexes of many classes of compounds were compiled. Ardrey et al. (2Y) compiled retention indexes of 1318 compounds of toxicologically interest on SE-30 or OV-1 stationary phase. Tanaka et al. (39Y) reported retention indexes of 163 metabolically important organic acids in the form of methylene units as trimethylsilyl derivatives, on 10% OV-1 and 10% OV-17 liquid stationary phases. Retention indexes of 24 thiolic acid esters (13Y) were also measured at 130 OC on 5% Apiezon M, OV-17, Triton X-305, and PEG 1OOO. Bredael(4Y) tabulated Kovats retention indexes for nearly 200 hydrocarbons at 0-200 "C on SE-30 capillary columns. Foster et al. ( 1 0 3 determined retention indexes of 77 diterpene resin acids on six liquid stationary phases (Silar 10 C, BDS, SP-2330, SP-lOOO,SE-54, and SE-30) by glass capillary GC. Retention indexes for polycyclic aromatic hydrocarbons, polycyclic aromatic sulfur, and nitrogen-containing compounds were also given (40Y). Kovats retention indexes of trimethylsilylated amino acids on SE-54, SP-2100, and carbowax-20M were measured by using n-alkanes as standards (11Y). Kovats retention indexes of several classes of pharmaceuticals, including amines, esters, pyridine derivative, imidazales,etc., on 5% SE-30,5% Apiezon L, and 3% neopentylglycolsuccinatewere also tabulated (6Y). Applications of Kovats retention indexes were reported for the identification of aromatic hydrocarbons as pyrolytic product of petroleum (19),the products of chlorination of decane (19Y), and the volatiles in the forensic and clinical toxicology (12Y). Drug screening via retention indexes of 175 basis drugs which were reproducible to within 4 index units of library values was described (1Y). The combined use of retention indexes and selective or specific detection techniques provides a powerful analytical approach to the identification or confirmation of complex mixtures. The reliability of the identification increases by use of functional groups or elements specific detections. The combined use (43Y) of the retention indexes on SE-30, Wax-51, Siponate DS 10,and OV-215 and the relative response factors of a photoionization detector (PID) to a flame ionization detector (FID) provide positive identification of various chemical classes of compounds such as aldehydes, ketones, esters, aromatics, cycloalkanes, cycloalkenes, ethers, cyclic ethers, halogenated compounds, alcohols, nitriles, nitrohydrocarbons, and double bond in aldehydes, esters, and alcohols. By using a variable-energy PID (9.5, 10.2, or 11.7 eV), alkanes, alkenes, and aromatic and polyaromatic hydrocarbons can be identified (7Y). Selective electron-capture sensitization with N20and O2 doping aids in the identification of phenolic compounds in oil shale waste water fraction (44Y) and of structural isomers (5Y). The combined use of gas chromatography and Fourier transform IR spectroscopy (GC/FTIRe provides an important and powerful tool to the identification of complex mixtures. Techniques for accurate assignment of Kovats retention indexes for GC/FTIR data obtained by using deuterated retention markers were described (15Y). The capability of GC/FTIR to identify toxic substances in environmental sample extracts was discussed (143. Gas chromatography mass spectrometry data system was also used in the identi ication of complex mixtures such as the neutral components in marijuana and tobacco smoke condensates (31Y), coal-derived liquid (32Y),urinary steroids (41Y), pesticide metabolites, and pesticide residues (163, etc. Comparison of the retention indexes as well as mass spectra made it possible to identify thiols of liquified gas (45Y). In addition to the use of retention indexes for the identification
1
190R
ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
of column eluents, the techniques of fingerprint and pattern recognition could also provide useful qualitative confirmation of complex mixtures. The use of electron-capture detector (ECD) and flame ionization detector (FID) fingerprint techniques for the evaluation of total volatile organic pollutants in river water and ground water was reported (33Y). Fingerprinting and characterization of carboxylic acids in in situ oil shale retort and process waters by capillary column GC-MS were described (9Y). A standarized operating condition required for the reproducible fingerprinting of essential oil by programmed temperature gas chromatography using packed columns was given (18Y). Jellum et al. (20Y) reported the application of capillary GC and pattern recognition for the analysis of the metabolic profiles of brain biopsies. The combined use of high-resolution two-dimensional electrophoresis, capillary GC-MS, and pattern recognition techniques gives the possibility of the classification of cancer cells on the basis of differences in their biochemical compositions. A computerized GC-MS as a tool for automated pattern recognition was described by Bertsch et al. (3Y). Pattern recognition for analysis of cigarette smoke (17Y), pyrolysis GC of microorganisms (28Y), high molecular weight organic compounds (29Y), and gasoline in tissues (37Y) were also reported. Quantitative Analysis. A general review of the problems of quantitation in trace analysis by gas chromatography was given by Novak (212). Key parameters affect quantitative precision by using open tubular column GC were discussed by Purcell(222). The function of the various sample introduction systems and the design and proper utilization of the capillary GC instrumentation were elaborated (222). Quantitative performance of various sampling techniques and the fast quantitative analysis of a sample containing 11 components in 30 s were demonstrated (222). In trace analysis, the enrichment technique of adsorption trapping of solute molecules on a bonded hydrophobic phase in a capillary column allowed on-column injection of up to 400 pL of sample and achieve part-per-trillion level of detection with an electroncapture detector (372). Ettre (42) also reviewed the purgeand-trap method and equilibrium headspace techniques as sample enrichment methods for enhancing the detection limits of gas chromatography to the part-per-trillion level. The use of nonvaporized on-column sampling technique for quantitative analysis by capillary column GC has grown in its acceptance as a nondiscriminative method for wide volatility range and thermally labile samples. The solutions for eliminating the distortion and peak splitting phenomena for large sample volume (>1pL) cold on-column injection were proposed (82,122,302,332,352). Grob et al. (82)described the preparation of a "retention gap" in capillary column inlet to prevent the flooding of stationary liquid phase. Yang (122, 352) discussed the role and the utilization of the solute focusing technique for preventing liquid sample flooding problems associated with on-column injection of large sample size in trace analysis. A temperature programmable on-column injector (12,132)which allows the injection zone temperature be programmed independently from the column oven was demonstrated to allow nondistorted peak profile for sample size up to 8 WLwith on-column solute focusing injections. Roeraade and Blomberg (262) reported an enrichment procedure for volatile trace components from a solvent or a gas employing a simultaneous chromatography and evaporation process of the solvent from a capillary tube. Capillary GC quantitative trace analysis is expected to grow in interest and importance. Recent advances in fused-silica capillary GC/MS direct interfacing techniques (72, 142, 342) allow quantitative transfer of sample from the column to the ion source of a mass spectrometer and permits analysis of highly labile compounds. It brings the detection level for an alcohol solution of nicotine to 50 times by changin the modifiers concentration from 0-1% in COz mobile p ase. For involatile samples analysis Futrell et al. (4") investigated the use of a supercritical fluid chromatography/MS system and concluded that a dense gas chromatography/mass spectrometer system did not have the reliability for nonvolatile compound analysis. On-line supercritical fluid chromatography Fourier-transform infrared spectrometry was demonstrate for the first time (8"). The system composed of a wide-bore fused-silica capillary column and an UV detector, FTIR flow cell, and flame ionization detector integrated in series. The IR transparency of COz just above the critical pressure makes it a nearly ideal solvent, but some adsorption bands intensify dramatically as the pressure is increased. Results show that easily identifiable spectra may be obtained of 3 pg each of anisole, acetophenone, and nitrobenzene injected into the chromatograph. The use of fluorescence detector in supercritical fluid chromatography was also investigated (2HH, 6"). A novel fiber optic aided detector design eliminates most background noise and reaches a detection limit as low Coupling of a supercritical fluid column to as 2 pg (2"). a flame ionization (FID) and nitrogen thermionic detector was studied by Fjeldsted et al. (3"). A microbore fused-silica restrictor was used to maintain pressure in the analytical column and to expand the effluent into the detector flame jet. The major problem in the utilization of flame-based detectors in SFC is the cluster formed at the flame tip which results in spiking of the detector signal and background. By electronically filtering the higher frequency component of the detector signal, the major portion of the spiking could be eliminated. Capillary column SFC-MS (IOHH, 11") has potential advantages over high-performance liquid chromatography-MS due to mobile-phase volatility and the easiness in direct interfacing. The chemical ionization source provides both good sensitivity and flexibility by the addition of different CI reagent gases. For 100-pm fused-silica column at optimum flow rate, and added gas can amount to as much as 90% of the CI reagent gas. The potential variation of the CI source pressure due to pressure programming of the SFC column was prevented by using an auxiliary gas inlet and servo valve to provide optimum and constant chemical ionization conditions regardless of column pressure.
E
d
LITERATURE CITED INTRODUCTION (IA) Rlsby, T. H.; Fleld, L. R.; Yang, F. J.; Cram, S. P. Anal. Chem. 1982, 54, 410R-428R. (2A) Aldert and Sutcllffe "The 1983-86 Market for Analytlcal Instruments"; Centcom, Ltd.: Westport. CT, 1983. COLUMNS Column Theory and Techniques (18) Acree, W. E., Jr. J . Chromatogr. 1983,257(2), 189-95. (28) Alvarez, R., Dominguez, J. M., Coca, J. Chromatographla 1983, 17(3), 186-8. (38) Arancibia, E. L.; Catoggio. J. A. J . Chrometogr. 1982,238(2), 281-90. (48) Buryan, P.; Macak, J. J . Chromatogr. 1982,237(3), 381-8. (58) Buys, T. S.; Wagener, J. 8.. HRC & CC, J . High Resolution Chromatogr. Chromatogr. Commun. 1982,5(12), 662-7. (68) Castello, G. Relata Tech. 1981, 13(29), 53-60. (78) Conder, J. R.; Rees, G. J.; McHale, S. J. Chromatogr. 1983, 258, 1-10. (8B) Gavrllina, L. Ya.; Zheivot, V. I.; Emalyanov, I. D. Chromatographla 1983, 17(2), 75-8. (98) Doleial, 8.; Holub. R. Chem. Llsty 1982, 76(4), 362-74. (IOB) Gelbln. D.; Wolff, H. J.; Frledrich, S. AIChEJ. 1982,28(2), 177-182. (118) Grec, J. J.; Devallez, 8.; Gulon, J. C. R , Seances Acad. Scl., Ser. 2 . 1982,295(7), 713-6. (128) Haken, J. K.; Srisukh, D. J. Chromatogr. 1081,219(1), 45-52. (138) Hou, J.; Wang, L. Fenxl Huaxue 1981,9(5). 524-9. (148) Jover, B.; Juhasz, J.; Szabo, 2. Magy. Kem. Foly. 1982, 88(11), 492-6. (158) Kaizuma, H. Anal. Chem. 1982,54(4), 732-6. (168) Katsanos, N. A.; Karalskakis, G. J . Chromatogr. 1983. 254, 15-25. (178) Karlln, 1. P.; Sukhorukov, 0. A. Zh. Fiz. Khlm. 1982, 56(4), 999-1001, (18B) Katsanos, N. A.; Karaiskakls, G.; Vattls, D.; Lycourghlotis, A. Chromatographla 1981, 14(12), 895-8. (198) Llu, T.; Wang. F. Huaxue Xuebao (Zengkan) 1981. 145-52. (208) Moody, H. W. J . Chem. €doc. 1982,59(4), 290-1. (218) Novak, J.; Vejrosta, J.; Roth, M.; Janak, J. Adv. Chromatogr. 1080, 15, 209-216. (228) O'Rellly, J. E. J. Chromatogr. 1982,238(2), 433-444. (238) Pacholec, F.; Poole, C. F. Anal. Chem. 1982,54(5). 1019-21.
(248) Roth, M.; Novak, J. J. Chromatogr. 1982,234(2), 337-45. (258) Suetaka, T.; Munemori, M. Nlppon Kagaku Kalshl 1982,(12), 1924-6. (268) Tlley, P.. F. Faraday Symp. Chem. SOC. 1981, 15, 93-102. (278) Thumneum, P.; Hawkes, S. Chromatograph& 1881, 14(10), 576-8. (288) Wetton, 8.;Goedert, M.; Lyons, T. ferkln-€/mer Chrom. News/. 1981, 9(2), 56-60. (298) Wlnskowskl, J. Chromatograph& 1983, 17(13), 160-5. LIOUID PHASES (1C) Berezkin, V. 0.; Allshoev, V. R.; Viktorova, E. N.; Gavrichev, V. S.; Fateeva, V. H. J. High Resolut. Chromatogr. Chromatogr. Commun. 1983,6(1), 42-4. (2C) Berezkin, V. G.; Georglev, 0. Izv. Khim. 1982, 15(1), 3-26. (3C) Bocquet, J. F.; Pommier, C. J . Chromatogr. 1983, 261(1), 11-32. (4C) Castello, G.; D'Amato, G. J . Chromatogr. 1983,254, 69-82. (5C) Chang, Sh. Ch,; GII-Av, E. J . Chromatogr. 1982,235(1), 87-108. (6C) Daft, J. L. Bull. Envlron. Contam. Toxicol. 1983,30(4), 492-6. (7C) De Beer, J. 0.; Heyndrlckx, A. M. J. Chromatogr. 1982, 235(2), 337-42. (8C) Dhanesar, S. S.; Poole, C. F. J . Chromatogr. 1982,252, 91-9. (9C) Dhanesar, S. C.; Poole, C. F. J . Chromatogr. 1982,253(2), 255-9. (IOC) Dhanesar, S. C.; Poole, C. F. Anal. Chem. 1983, 55(9), 1482-5. ( l l C ) Doerlng, C. E.; Stevenz, D.; Schroeter, P. Z. Chem. 1981,21(10), 386-7. (12C) Fu, R.; Wu., W.; Tlan, L. Huaxue Shy/ 1982,4 ( 5 ) , 270-3. (13C) Ingraham, D. F.; Shoemaker, C. F.; Jennings, W. J. Chromatogr. 1982,239, 39-50. (14C) Inui, T.; Murakaml, Y.; Suzuki, T.; Takegaml, Y. folym. J . (Tokyo) 1982, 14(4), 261-8. (15C) Koenig, W. A.; Francke, W.; Benecke, T. J . Chromatogr. 1982,239, 227-31. (16C) Koenig, W.; Benecke, T.; Ernst, K. J. Chromatogr. 1982, 253(2), 267-70. (17C) Koenig, W. J High Resolut Chromatogr Chromatogr Commun . 1982,5(1 I), 588-95. ( l a c ) Kong, R. C.; Lee, M. L.; Tominaga, Y.; Pratap, R.; Iwao, M.;Castle, R. N. Anal. Chem. 1982,54(11), 1802-6. (19C) Markldes, K.; Blomberg, L.; Buljten, J.; Wannman, T. J . Chromatogr. 1883,254, 53-81. (20C) 01, N.; Dol., T.; Kitahara, H.; Inda, Y. J. Chromatogr. 1982, 239, 493-98. (21C) 01, N.; Dol, T.; Kltahara, H. Sumltomo Kagaku Tokushugo 1982, 1 , 17-25. (22Cj Oesterhelt, G.; Marugg, P.; Rueher, R.; Germann, A. J . Chromatogr. 1982.23411). 99-106. (23C) Patte,' F.; Etcheto, M.; Laffort, P. Anal. Chem. 1982, 54(13), 2239-47. (24C) Petsev, N. I z v . Khim. 1982, 15(1), 102-113. (25C) Poole, C. F.; Butler, H.; Agnello, S. A,; Sye, W. F.; Zlatkis, A.; Holzer, G. J . Chromatogr. 1981,217, 39-50. (26'2) Sakagaml, S.; Nakamizo, M. J. Chromatogr. 1882,234(2), 357-63. (27C) Singliar, M.; Macho, V. Chem. Zvestll981, 35(5), 681-70. (28C) Slngilar, M. Petrochemla 1982,22(4), 114-9. (29C) Slngllar, M.; Macho, V. Petrochem& 1982,22(4), 97-108. (30C) Sojak, L.; Kraus, 0.; Ostrovsky, J.; Kralovlcova, E.; Farkas. P. J. Chromatogr. 1081,219(2), 225-34. (31C) Sojak, L.; Kraus, G.; Ostrovsky, J.; Kralovicova, E. J . Chromatogr. 1982,234(2), 347-56. (32C) Stolyarov, 8. V.; Kartsova, L. A. Vestn. Lenlngr. Unlv., Flz. Khim. 1982,(I), 88-94. (33C) Sldorov, R. I. Zh. Flz. Khlm. lg82,56(5), 1057-64. (34'2) Vaierlo, F.; Bottino, P.; Cimberie, R. Anal. Chem. Symp. Ser. (Chromatogr. Mass Spectrom. Blomed. Scl., 2) 1883, 14, 221-31. (35C) Vigdergauz, M. S.; Bankoskaya, T. R. Usp. Gazov. Khromatogr. 1982,6 , 136-46. (36C) Watabe, K.; Hobo, T.; Suzukl, Sh. J . Chromatogr. 1982, 239, 499-505. (37C) Witkiewicz, 2. J . Chromatogr. 1982,251(3), 31 1-37. (38'2) Zoccolillo, L.; Cartonl, G.; Lozzl, L. J. Chromatogr. 1982, 236(2), 339-44. (39C) Xiao, Y.; Li, G.; Yan, R. Huadong Xueyan Xuebao 1981,(3), 33-41.
.
.
.
.
SOLID SUPPORTS (ID) Andronlkashvlll, T. 0. Laperashviil, L. Ya; Kvernadze, T. K. I z v . Akad. Nauk Gruuez. SSR, Ser. Khlm. 1981, 7(3), 224-30. (2D) Andronlkashvili, T. G.; Kvernadze, T. K., Ya; Skhlrtladze, N. I. Soobshch. Acad. Nauk Gruz. SSR 1982, 106(2), 305-8. (3D) Anhang, J.; Gray, D. V. Physlcochem. Aspects fo/ym. Surf. [ f r o c . I n t . Symp.] 1981 (pubilshed 1983), 2, 659-67. (4D) Burba, J. L. U.S. Patent 4321 065, March 1982. (5D) Chen, X. Huaxue Shill 1981,(4), 251-2. (8D) DlPaola-Baranyi, G. folym. Prep. Am. Chem. SOC., Dlv. Polym. Chem. 1980,21(2), 214-15. (7D) DJordJevic,N. M.; Kopecnl, M. M. Glas. Hem. Drus. Beograd 1981, 46(9), 471-7. (8D) Feltl, L.; Antoninova, M.; Smolkova, E. Collect. Czech. Chem. Commun. 1982. 47(2), 576-81. (9D) Feiti, L.; Hronkova, J.; Smolkova, E. Collect. Czech. Chem. Commun. 1982,47(2), 582-7. (10D) Galln, M. Eur. fo/ym. J . 1983, 19(1), 1-4. (11D) Hlllerova, E.; Jlratova, K.; Zdrazii, M. Appl. Catal. 1981, 1(6),343-54. (12D) Ito, K. Kobunshl 1982,31(3), 227-31. (13D) Korol, A. N.; Dovbush, T. I. J. Chromatogr. 1982, 238(2), 291-6. (14D) Langvardt, P. W.; Ramstad, T. J . Chromatogr. Sci. 1981, 19(10), 536-42. ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
193R
GAS CHROMATOGRAPHY (15D) Laperashvlll, L. I.;Babayan, S. G.; Kostandyan, M. N. Soobshch. Akad. Nauk Gruz. SSR. 1082, 107(1). 65-6. (l6D) Naito, K.; Endo, M.; Morlguchl, S.; Takel, S. J. Chromatogr. 1882, 253(2), 205-18. (17D) Palmal, G.; Olah., K.; Noszticzius, 2. Magy. Kem. Foly. 1982, 88(5), 202-210. (18D) Picker, J. E.; Slevers, R. E. J. Chromatogr. 1881, 277, 275-88. (19D) Popl, M.; Horejs, J.; Voznakova, 2.; Coupek, J. Sb. Vys. Sk. Chem.-Techno/. Praze 1981, H-16, 133-48. (20D) Prokopeva, M. F.; Tadzhleva, N. Kh.; Silklna, T. V.; Glazunova, L. D.; Sakodynskll, K. I.Zh. Anal Khim. 1982, 37(5), 930-4. (21D) Rousseva, N. Dokl. 60lg. Akad. Nauk 1082, 35(12), 1677-80. (22D) Saint Flour, C.; Paplrer, E. Ind. Eng. Chem. Prod. Res. Dev. lg82, 21(2), 337-41. (23D) Sakodynskll, K. I.Zh. Uses. Khlm. 0-va 1983, 28(1), 34-43. (24D) Sugll, A.; Harada, K.; Toblno, T. J. Chromatogr. 1983, 254, 270-6. (25D) Suzukl, T.; Murakaml, Y.; Inul, T.; Takegaml, Y. Polym., J. (Tokyo) 1981, 13(11), 1027-35. (260) Suprynowlcz, Z.; Tracz, E. J . Chromatogr. 1982, 237(1), 49-56. (27D) Shadrina, N. E.; Kleshcheva, M. S.; Ullnskaya, N. N. Zh. Anal. Khim. 1982, 37(4), 679-82. (28D) Schuchmann, H. Kontakte (Darmstadt) 1981. (3), 13-15. (29D) Takahara. Y.; Ohno, K.; Hayakawa, T. Gifu-ken Kogal Kenkyusho Nenpo 1880, 9,33-35. (30D) Zhubanov, B. A.; Arkhlpova, I. A.; Kan, I.I.; Kim, L. V.; Mashkevlch, S. A.; Suvorov, B. V. U.S.S.R. Patent SU956001, Sept. 1982, SORPTION PROCESSES AND SOLVENTS (IE) Andronikashvlll, T. G.; Strllchuk, L. V.; Banakh, 0. S. Soobsch. Akad. Nauk Gruz. SSR 1883, 109(2), 313-316. (2E) Anhang, J.; Gray, D. G. J. Appi. Polym. Scl. 1982, 27(1), 71-81. (3E) Asaka, M.; Hotta, M.; Torll, K. Tohoku Kogyo GJutsu Shikenso Hokoku 1982, 15, 54-60. (4E) Avgul, N. N.; Kovaleva, N. V.; Maryashln. I.L.; Mlshlna, G. A. Koiloidn. Zh. 1982, 44(2), 311-14. (5E) Barvenko, V. V.; Muganllnskll, F. F.; Lyushin, M. M.; Usenko, M. I.Azerb. Kim. Zh. 1982, 4, 113-16. Evteeva, V. A.; Kovaleva, N. V.; Lopatkln, A. A. Kollodn. (6E) Berezln, G. I.; Zh. 1981, 43(4), 1151-5. Tarasevlch, Yu. I.J . Chromafogr. (7E) Bondarenko, S. V.; Zhukova, A. I.; 1982, 241(2). 281-6. (8E) Gawdzlk, B.; Zuchowskl, 2.; Matynla, T.; Gawdzlk, J. J . Chromatogr. 1982, 234(2), 365-72. (9E) Glordano, N.; Cavallaro, S.; Antonuccl, P.; Van Truong, N.; Bart, J. C. J. 2.Phys. Chem. (Le/pz/g) 1981, 262(6). 996-1008. (10E) Harada, K.; Sugll, A. Bunseki Kagaku 1982, 31(11), 628-31. (11E) Harada, K.; Ogawa, N.; Fujlta, I.Bunseki Kagaku 1982, 37(12), 697-701. (12E) Hoppe, H.; Worch, E. Chem. Tech. (Leipzig) W81, 33-(ll), 572-5. (13E) Hu, J.; LI, Q.; Chen, H. Culhua, Zuebao 1981, 2(3), 217-223. (14E) Igarashl, A.; Oglno, Y. Appl. Catal. 1982, 2(6), 339-45. (15E) Katsanos, N. A. J. Chem. Soc., faraday Trans. 1982, 78(4), 1051-63. (16E) Klselev, A. V.; Polotynuk, E. 8.; Shcherbakova, K. D. Chromatographla 1981, 74(8),478-83. (17E) Maslowska, J.; Bazylak, G. Chromatographla 1983, 77(4), 191-4. (ME) Mlhalla, G.; Ababl, V.; Naum, N. Rom. Patent R070756, Jan. 1977. (l9E) Molder, L.; Metlitskaya, 0. EesfiNSVTead. Akad. Tolm. Keem. 1982, 37(4), 296-8. (20E) Rlmatori, V.; Carelll, G. J . Work. Environ. Health IS82, 8(1), 20-3. (21E) Sellm, M.; Parcher, J. F.; Lln, P. J J . Chromatogr. 1982, 239, 411-21. (22E) Slu, K. W. M.; Fraser, M. E.; Berman, S. S. J . Chromafogr. 1883, 256(3), 455-9. (23E) Stukelman, E. 8. Deposited Doc. 1981, VINITI 316781, 138-9. (24E) Subbarao, K. V.; Damodaran, N. P.; Dev. S. J. High Resoiut. Chromatogr. Chromatogr. Commun. I W 1 , 4(11), 583-4. (25E) Uemlchl, Y.; Ayame, A.; Kashlwaga, Y.; Kanoh, H. J . Chromafogr. 1983, 259(1), 69-77. (26E) Vlasenko, E. V.; Gavrllova, T. B. I z v . Khim. 1982, 15(1), 129-34. (27E) Zhukova, A. I.; Bondarenko, S. V.; Tarasevlch, Yu. I . Kolloidn. Zh. 1981, 43(6), 1068-75. OPEN TUBULAR COLUMN GAS CHROMATOGRAPHY Theory and Techniques (1F) Annlno, R. L.; Leone, J. J. Chromatogr. Scl. 1982, 20(1), 19-26. (2F) Bengtsson, 0.; Cavallln, C. J. Chromatogr. 1982, 240(2), 488-90. (3F) Eerezkin, V. G.; Vasln. L. S.; Gavrlchev, V. S.; Llpavski, V. N. Zavod. Lab. 1983, &(I), 23-5. (4F) Buser, H. U.; Soder, R.; Wldmer, H. M.; J. High Resolut. Chromatogr. Chromafogr. Commun. lg82, 5(3). 156-7. (5F) . . Bush, B.: Connor. S.; Snow, J. J. Assoc. Off. Anal. Chem. lS82, 65(3), 555-66. (6F) Calder, A. G. J. H/gh Resoluf. Chromafogr. Chromatogr. Commun. 1982. 5(6I. ~.,.324. -~ (7F)-Dkz-Masa, J. C.; Nleto, M. I.; Oteo, J. L.; Dabrlo, M. V. An. Quim. Ser. C. 1982, 78(1), 79-85. (8F) Friedll, F.; Zlmmeli, B. Mift. Geb. Lebensmiltelunters. Hyg. 1982, 73(3), 357-61. (9F) Garbuzov, V. G.; Vasllev, A. V.; Golovnya, R. V. I z v . Akad. Nauk SSSR, Ser. Khim. 1982, (3), 611-16. (IOF) Gregorlev, 0. Izv. Khlm. 1982, 15(1), 78-84. (11F) Grob, K.; Grob, G.; Blum, W.; Walther, W. J. Chromatogr. 1982, 244(2), 197-208. (12F) Grob, K., Jr. J. Chromafogr. lg82, 237(1), 15-23. (13F) Grob, K., Jr.; Neukom, H. P. J . Chromafogr. 1982, 236(2), 296-306.
.
194R
ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
(14F) Graydon, J. W.; Grob, K. J. Chromafogr. 1983, 254, 265-9. (15F) Grob, K., Jr. J. Chromatogr. 1982, 251(3), 235-48. (16F) Herlller, F. Lyon Pharm. 1981, 32(6), 335-41. (17F) Huang, J. Ch.; Madey, R. J. Chromatogr. Scl. 1982, 20(5), 216-220. (18F) Janssen, F.; KalMln, T. J . Chromatogr. lg82, 235(2), 323-336. (19F) Janssen, F.; Kalldln, T. J. Hlgh Resolut. Chromatogr. Chromatogr. Commun. 1982, 5(2), 107-8. (20F) Khromchenko, Ya. L.; Rudenko, B. A. Zh. Anal. Khim. 1981, 36(10), 2000-5. (21F) Kocsl, E.; Balla, J.; Kaufman, B. E. Magy. Kem. foly. 1982, 88(12), 556-9. (22F) Komarek, K.; Hornova, L.; Churacek, J. J. Chromafogr. 1982, 252, 293-6. (23F) Korhonen, I.0. J. Chromatogr. 1985, 257(1), 122-6. (24F) Krupclk, J.; Mocak, J.; Slmova, A.; Garaj, J.; Guiochon, G. J. Chromatogr. W82, 238(1). 1-12. (25F) Llpsky, S. R.; McMurray, W. J. J. Chromafogr. 1982, 239, 61-9. (26F) Marrlot, P. J.; Gill, J. P.; Egllnton, G. J . Chromatogr. 1982, 236(2), 395-401. (27F) Mayr, M.; Lorbeer, E.; Kratzl, K.; J. Am. OllChem. SOC. lg82, 59(1), 53-7
Moncur, J. G. J. High Resolut. Chromafogr. Chromatogr. Commun. 1082, 5(1), 53-5. (29F) Olacsi, I.; Plnke, F. L.; Takacs, J. Magy. Kem. Foly. 1982, 88(10), 456-8. _. (30F) Olsen, N. B. Dan/ Keml. 1982, 63(10), 276-8. (31F) Onuska, F. I.; Komlnar, R. J.; Terry, K. A. Capillary Chromatography (5th Symp. Proceedings) 1983, 160-8, Rlva dai Garda, Italy. (32F) Plotczyk, L. L.; Larson, P. J. Chromatogr. 1983, 257(2), 211-26. (33F) Rudenko, B. A.; Khromchenko, Ya. L. Zh. Anal. Khim. 1982, 37(1), 99- 109. (34F) Saito, H. J. Chromatogr. 1982, 243(2), 189-206. (35F) Schomburg, G.; Husmann, H.; Ruthe, S.; Herralz, M. Chromatographla 1982. 1519). 599-610. (36F) Schujes, c. P. M.; Varmeer, E. A,; Rljks, J. A.; Cramers, C. A. J. Chromafogr. 1982, 253(1), 1-16. (37F) Shlmlzu, Y. Kogai Shigen Kenkyusho I h o 1981, 71(2), 23-7. (38F) Tersac, G. Bull. SOC. Chlm. f r . 1982, (1-2 Pt.2), 59-64. (39F) Traltler, H.; Rossler, M. J. High Resoiuf. Chromatogr. Chromatgr. Commun. 1982, 5(4), 189-91. (40F) Vlnet, B. Clln. Chem. 1983, 29(3). 452-5. (41F) Volkov, S. M.; Goryaev, V. M.; Anlkeev, V. I.; Vashuk, V. V. Patent SU967550, 1982. (42F) Wright, B. W. Dlss. Absfr. I n f . 6 1982, 43(6), 1837-8. (28;)
INSTRUMENTATION (1G) Ahlstrom, R. c., Jr.; Johnson, M. S.; Moore, J. R.; Schoppe, I. R., Jr. U.S. Patent 4359891. 1962. (26) Baechmann, K.; Hamm, V.; Werner, A.; Tschoepl, P.; Toelg, Dev. At. Plasma Spectrochem. Anal. Proc. Int. Winter Conf. 1980, 361-8. (3G) Balm, M. A.; Schuetze, F. J.; Frame, J. M.; Hill, H. Jr. Am. Lab. 1982, 74(2) 59-61, 64, 66, 68, 70. (40) Bayer, E.; Llu, 0. H. J. Chromafogr. 1983, 256(2), 201-12. (5G) Bellabes, R.; Granger, R.; Vergnaud, J. M. Sep. Sci. Techno/. 1882, 17(9), 1177-82. (6G) Chen, Y.; Wu, Q.; Shen, G. Huagong Xueyan Xuebao 1881, (4), 59-67. (7G) Chlosta, W.; Pospll, P. Ger. Offen. DE 3,130245, Feb. 1983. (8G) Comberbach, D. M.; Bu Lock, J. D. Chromatogr. Newsi. 1982, 10(1), 19-23. (9G) Corklll, J. A.; Jopplch, M., Kuttab, S. H.; Glese, R. W. Anal. Chem. lg82, 54(3), 481-5. (1OG) De Forest, R.; Rothchlld, R. J . Chromatogr. Sci. 1983, 21(2), 94-6. (11G) Dong, M. W. Chromatographia 1081, 14(8),447-51. (12G) Drost, D. J.; Fenster, A. Med.Phys. lg82, 9(2), 224-30. (13G) Drost, J.; Novak, J. Inf. J. Envlron. Anal. Chem. 1982, 17(3-4), 241-9. (14G) Eckhoff, M. A.; Mc Carthy, J. P.; Caruso. J. A. Anal. Chem. 1982, 54(2), 165-8. (15G) Hines, J. W.; Erlckson, M. D.; Newton, D. L.; Moseley, M. A.; Retzlaff, L. M.; Pelllzzarl, E. D. Hlgh Res. Chromatogr. Chromatogr. Commun. 1982, 5(1), 52-3. (16G) Estes, S. A.; Uden, P. C.; Barnes, R. M. J. Chromafogr. 1982, 239, 181-9. (17G) Foerst, D. L. Gov. Rec. Announce Index 1981, 81(22), 4690. (18G) Garlock, S. E.; Adams, G. E.; Smith, S. L. Am. Lab. 1982, 14(12), 48-55. (19G) Gauthler, M.; Pllon, R.; Kutschke, K. J. Chromatogr. Sci. 1982, 20(6), 283-5. (20G) Green, R. Anal. Chem., 1983, 55(1), 20A-22A, 25A-26A. 28A, 30A, 32A. (21G) Greter, J.; Staale, 0. Anal. Chem. 1982, 54(9), 1646-7. (220) Gulllemln, C. L. J . Chromatogr. 1982, 230,363-76. (230) Hammer, C. G. V. J . Chromatogr. 1982, 249(1), 167-73. (24G) Hanal, Y.; Katou, T.; Ilzuka, T.; Yokahama Kokurlfsu Dalgaku Kankyo Kagaku Kenkyu Senfa Klyo 1982, 8(1), 57-62. (250) Heil, C. Report 1980, LPNHEXT-80-03, P 155, Palaiseau, France. (26G) Hlrazumi, K.; Shirato, K.; Kawashlma, K. Ger. Offen. DE 3,11672, Nov. 1982. (27G) Holllngworth, T. A,, Jr.; Jhrom, H. R. J. food Sci. 1983, &(I), 290-1. (28G) Hu, Zh., Ch.; Wu, H. Youji Huaxue 1882, (2), 139-41. (29G) Ingraham, D. F.; Shoemaker, C. F.; Jennlngs, W. J. High Res. Chromafogr. Chromatogr. Commun. 1982, 5(5), 227-35. (30G) Joensson, J. Q.; Vejrosta, J.; Novak, J. J. Chromafogr. 1982, 236(2), 307- 12. (31G) Joensson, J. A.; Mathlasson, L. J. Chromatogr. 1981, 219(3), 427-30.
GAS CHROMATOGRAPHY (32G) Kahlhlra, N.; Maklno, K.; Klrlta, K.; Watanabe, Y. J. Chromatogr. 1982, 239, 617-24. (33G) Kebelmann, L.; Seefeld, F.; Tunkel, W. East Ger. DD 151817, Nov. 1981. (34G) Kettrup, A. Trends Anal. Chem. 1982, 7(6), 142-5. (350) Kline, B. J.; Solne, W. H. Drugs fharm. Scl. 1981, 1 7 , 1-103. (360) Kolarovlc, L.; Traltler, H. J. High Res. Chromatogr. Chromatogr. Commun. 1981, 4(10), 523-4. (37G) Krlchmar, S . 1.; Podolskll, A. A.; Eflrnstev, V. P. SV Patent 938 146, June 1982. (38G) Kosklnen, L. TrAC, Trends Anal. Chem. 1982, 7(14), 324-8. (39G) Krlshnen, K.; Brown, R. H.; Hill, S. L. Int. Lab. 1982, 17(4), 66, 88-70, 72, 74-5. (40G) Kuster, T.; Wetzel, E. Int. J. Mass Spectrom. Ion fhys. 1983, 46, 173-6. (41G) Lahe, J. J. High Res. Chromatogr. Chromatogr. Commun. 1981, 4(11), 582. (420) Larsson, L. Anal. Chem. Symp. Ser. 1983, 13, 193-8. (43G) Lea, R. E.; Bramston-Cook, R.; Tschlda, J. Anal. Chem. 1983, 55(4), 628-9. (44G) McDonald, J. T.; Kalaslnsky, V. F. R o c . SfIE-Int. SOC. Opt. Eng. 1981, 289, 154-5. (45G) Merz, W.; Neu, H. J.; Panzel, H. Vom Wasser 1981, 57, 107-14. (46G) Mueller, R. K.; Wehren, H. J.; Beitr. Diagn. mer. Akuter Intox. Vortr. Sym. 4th 1982, 88-103. (470) Mague, T. H.; Sherman, P. L.,Jr. J. Chromatogr. Scl., 1982, 20(5), 225-7. (480) Markey. S. P.; Abramson, F. P. Syth. Appl. Isot. Labeled Compt. Proc. Int. Symp. 1982, 291-6. (49G) Massey, S. R.; Maylls, M. A,; Harris, P. GB Patent 1595872, Feb. 1978. (50G) Muret. P.; Lacaze. P. Corros. Sci. 1982, 22(4), 321-9. (51G) Munson, B. Int. Lab. 1981, 7 f ( 8 ) , 16-26. (52G) Ohls, K.; Sommer, D. Dev. At. Plasma Spectrochem. Anal. Proc. Int. Winter Conf. 1980, 327-36. (53G) Phllllps, R. J.; Krauss, K. A.; Freeman, R. R. High Res. Chromatogr. Chroimatogr. Commun. 1982, 5(10), 546-52. (540) Proske, M. G.; Bender, M.; Schomburg, G.; Hueblnger, E. J. Chromat q r . 1982, 240(1), 95-106. (55G) Purcell, J. M.; Magldman, P. Anal. Lett. 1983, 76(A6), 465-83. (56G) Rothchlld, R.; De Forest, P. R. J. High Res. Chromatogr. Chromatogr. Commun. 1982, 5(6), 321. (57G) Rosslter, V. Int. Lab. 1982, 72(5), 40-47. (58G) Schomburg. G.; Husmann, H.; Schultz, F.; J. High Res. Chromatogr. Chromatogr. Commun. 1982, 5(10), 565-7. (59G) Scott, R. P. W. TrAC. Trends Anal. Chem. 1983, 2(3), 1-11, V-VIII. (60G) Sistl, G.; Trestlani, S.; Rlva, E. Eur. Patent 58917, April 1982. (61G) Smith, S. L.; Garlock, S. E.; Adams, G. E. Appl. Spectrosc. 1983, 37(2), 192-6. (62G) Takayama, Y. J High Res. Chromatogr Chromatogr Commun . 1982, 5(4), 211-12. (63G) Takayama, Y. Unsekl K8gaku 1982, 37(10),597-601. (64G) Vogt, W.; Jacob, K.; Ohnesorge, A. 8.; Schwertfeger, G. J . Chromatogr. 1981, 217, 91-8. (65G) Wadhams, L. J. 2. Naturforsch C.,Blosci. 1982, 37C(lO), 947-52. (66G) Wang, F. S.; Shanfleld, H.; Zlatkls. A. Anal. Chem. 1982, 54(11),
.
.
.
.
1886-8.
(67G) Wang, F. S.; Shanfleld, H.; Zlatkls, A. Anal. Chem. 1983, 55(2), 397-8. (68G) Yokogawa Electric Works, Jpn. Kokai Tokyo Koho JP82 13355, Jan. 1982. HIGH-RESOLUTION COLUMNS AND APPLICATIONS (1H) Abe, I.; Kuramoto, Sh.; Musha, S . J. Chromatogr. 1983, 258, 35-42. (2H) Ahnoff, M.; Ervlk, M.; Johansson, L. Proc. Int. Symp. Capillary Chromatogr., 4th, 1981, 487-504. (3H) Arrendale, R. J.; Severson, R. J.; Chortyk, 0. T. J. Chromatogr. 1983, 254, 63-8. (4H) Bartle, K. D.; Wright, B. W.; Lee, M. L. Chromatographia, 1981, 14(7), 387-97. (5H) Berezkin, V. G.; Korolev, A. A.; Budantseva, M. N.; Alishoev, V. R.; Popova, T. P.; Sorokina, E. Yu.; Flrsov, V. M.; Khodakovskll, M. D.; Gnatyuk, L. N. Zh. Anal. Chim. 1982, 37(5), 890-3. (6H) Blomberg, L.; Buljten, J.; Markldes, K.; Waennman, T. J. Chromatogr. 1982. 239, 51-60. (7H) Buijten, J.; Blomberg, L.; Markldes, K.; Waennman, T. J. Chromatogr. 1982, 237(3), 465-8. (8H) Burrows, R.; Cooke, M.; Gillesple, D. G. J. Chromatogr. 1983, 260(1), 168-72 ._ (9H) Evans, M. B.; Kawar, M. I.;Newton, R. Chromatographia 1981, 74(7), 398-402. (10H) Flnkelmann, H.; h u b , R. J. Report 1982, DOE/ER/10554-25, Order No. DE82020753, 22 pp. (11H) Fu, R.; Wu. W. Huaxue ShJi 1982, (I), 50-3. (12H) Fu, R.; Wu, W. Huaxue Shljl 1981, (4). 210-13. (13H) Golovnya, R. V.; Samusenko, A. L. J. Chromatogr. 1981, 277, 183-90. .. (14H) Grob, K.;Grob. G. J. High Res. Chromatogr. Chromatogr. Commun. 1982. 5(1), 13-18. (15H)Grob; K.; Grob, G. J. High Res. Chromatogr. Chromatogr. Commun. 1982, 5(3), 119-23. (16H) Grob, K. Jr.; Mueller, R. J. Chromatogr. 1982. 244(2), 185-96. (17H) Haeusler, K. G.; Benne, I.; Jobst, K. Pl8ste Kautsch. 1982, 29(1), 26-30. (18H) Hussein, M. M.; MacKay, D. A. M. J. Chromatogr. 1982, 243(1), 43-50.
(l9H) Janlnl, 0. M.; Ubeld, M. T. J. Chromatogr. 1982, 236(2), 329-37. (20H) Janssen, J. Chromatographia 1982, 75(1), 33-7. (21H) Jennlngs, W. G.; Wohleb, R. H.; Jenkins, R. G. Chromatographia 1981, 14(8), 484-7. (22H) Karl, I.; Huhtlkangas, A.; Gynther, J.; Vartlalnen, T.; Hlltunen, R. Chromatographia 1981, 14(8), 462-4. (23H) Kong, R. C.; Lee, M. L.; Tomlnaga, Y.; Pratap, R.; Iwao, M.; Castle, R. N.; Wise, S. A. J. Chromatogr. Scl. 1982, 20(11), 502-510. (24H) Kraus, 0.; Tran. Thi, H. V.; Weissflog, W. 2. Chem. 1982, 22(12), 448-9. (25H) Laster, W. G.; Pawliszyn, J. 6.; Phllllps, J. B. J . Chromatogr. Scl. 1982, 20(6), 278-82. (26H) Martln, M.; Jurado-Balzaval, J. L.; Gulochon. G.; C.R. Seances Acad. Sci. Ser. 2 1982, 295(4), 473-6. (27H) Medyantsev. V. E.; Shlyapova, G. A.; Shushunova, A. F. Khim. Drev. 1982, (3), 103-5. (28H) Nazarova, V. I.,Petrova. R. S., Shcherbakova, K. D. Izv. Khlm. 1982, 75(1), 27-35. (29H) Olsson, A. M.; Joensson, J. A. J. High Res. Chromatogr. Chromatogr. Commun. 1982, 5(1), 55-6. (30H) Onuska, F. I.: Mudrochova. A.; Terry, K. A. J. Great Lakes Res. 1083, 9(2), 169-82. (31H) Pretorlus, V.; Desty, D. H. Chromatographla 1982, 15(9), 569-74. (32H) Redant, G.; Sandra, P.; Verzele, M. Chromatogr8phia 1982, 75(I), '
.- . ..
1!LlA
(33H) Sandra, P.; Schelfaut, M.; Verzele, M. J. Hlgh Res. Chromatogr. Chromatogr. Commun. 1982, 5(1), 50-1. (34H) Springer, D. L.; Phelps, D. W.; Schlrmer, R. E. J. High Res. Chromatogr. Chromatogr. Commun. 1981, 4(12), 638-41. (35H) Tesarlk, K.; Komarek, K.; Hlavickova, H.; Chluacek, J. Chem., Listy 1981, 75(10), 1085-90. (36H) Tesarlk, K.; Komarek, K.; Rosenbergova, J.; Slavlk, V.; Churacek, J. Chem. Listy 1982, 76(5), 539-48. (37H) Vlgh, G.; Hlavay, J.; Varga-Puchony, 2 . ; Welsch, T. J. High Res. Chromatogr. Chromatogr. Commun. 1982, 5(3), 124-7. (38H) Verzele, M. J. High Res. Chromatogr. Chromatogr. Commun. 1982, 5(12), 685-6. (391-1) Welsch, T.; Mueller, R.; Engewald, W.; Werner, G. J. Chromatogr. 1982, 241(1), 41-6. (40H) Wright, B. W.; Peaden, P. A.; Lee, M. L. Chromatographla 1982, 75(9), 564-6. (41H) Zlatkls, A. NASA CR 1982, NASA-CR-187831, NAS 1.26.167631, 24 PP. (42H) PrOC. Int. Symp. Capillary Chromatogr., 5th, Riva del Garda, Italy, April 1983. DETECTORS
General (11) Drushel, H. V. J. Chrom. S d . 1083, 27, 375-84. (21) Hill, H. H., Jr.; Balm, M. A. TrAC, Trends Anal. Chem. 1982, 1(9),
206-10. (31) Hill, H. H., Jr.; Balm, M. A. TrAC, Trends Anal. Chem. 1982, 7(10), 232-6. (41) Leonhardt, J. W. Ind. Appl. Radioisot. Radiat. Techno/., froc. Int. C O U ~1981-1982, . 163-78, 271. (51) Lovelock, J. E. Pure Appl. fhys. 1982, 4 3 , 1-30. (61) Mantlca, E. Comm. Eur. Communities, [Rep.] EUR 1982, Anal. Org. Micro pollut. Water, 61-92. Thermal Conductivity Detectors (TCD) (IJ) Patterson, P. L.; Gatten, R. A,; Kolar, J.; Ontlveros, C. J. Chrom. Sci. 1982, 20, 27-32. (2J) Wells, G.; Simon, R. J. Chromatogr. 1983, 256, 1-15. Flame Ionlzatlon Detectors (FID) (1K) Albertyn, D. E.; Bannon, C. D.; Craske, J. D.; Hal, N. T.; O'Rourke, K. L.;Szonyl, C. J. Chromatogr. 1982, 247, 47-61. (2K) Berezkln, U. G.; Tsltslshvlll, G. V.; Andronlkashvlli, T. G.; Gveleslanl, 2. A. Izv. Akad. NaukGruz. SSR, Ser. Khim. 1982, 8(2), 121-6. (3K) Bolton, H. C. Aust. Phys. 1982, 19(8), 152-7. (4K) Head, M.; McAlllster, T. Aust. J. Chem. 1982, 35(8), 1743-6. (5K) Kokal Tokkyo Koho JP 57146155, 09 Sept. 1982. (8K) Kokal Tokkyo Koho JP 57146154, 09 Sept. 1982. (7K) Luethe, J.; Wlttkowski, W. Chem. Tech. (Le@@) 1983, 35(1), 32-4. (8K) McAllister, T. Int. J. Mess Spectrom. Ion fhys. 1983, 47, 187-90. (9K) McWllllam, I. G. Chromatographla 1983, 17 (5), 241-3. (10K) Nicholson, A. J. C. J. Chem. Soc., Faraday Trans. 7 1982, 78(7), 2183-94. (11K) Rodlonov, A. A. U.S.S.R. 940048, 30 June 1982. (12K) Thomason, M. M.; Bertsch, W.; Apps, P.; Pretorlus, V. J. High Resolut. Chromatogr. Chromatogr. Commun. 1982, 5, 690-92. (13K) Tsltslshvlll, G. V.; Berezkln, V. 0.; Andronlkashvili, T. G.; Gveleslanl, 2 . A. Izv. Akad. NaukGruz. SSR, Ser. Khim. 1982, 35(8). 1743-6. Electron-Capture Detectors (ECD)
(IL) Aue, W. A.; Slu, K. W. M. J. Chromatogr. 1982, 239, 127-44. (2L) Bengtsson, 0.; Cavallln, C. J. Chromafogr. 1982, 240, 488-490. (3L) Campbell, J. A.; Grlmsrud, E. P. J. Chromatogr. 1982, 243, 1-8. (4L) Campbell, J. A.; Grlmsrud, E. P.; Hageman, L. R. Anal. Chem. 1983, 55(8), 1335-40. (5L) Chang, L.; Zhu, A. FenxiHauzue 1982, 70(4), 210-13. (6L) Connolly, M. J.; Knighton, W. B.; Grimsrud, E. P. J. Chromatogr. 1983, 285. 145-57. . -(7L) Corklll, J. A.; Jopplch, M.; Kuttab, S. H.; Glese, R. W. Anal. Chem. 1982, 54, 481-5.
---.
ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
195R
GAS CHROMATOGRAPHY (EL) Dovichl, N. J.; Kelier, R. A. Anal. Chem. 1983, 55, 543-549. (9L) Goldan, P. D.; Fehsenfeid, F. C.; Phillips, M. P. J. Chromatogr. 1982, 239, 115-26. (1OL) Grimsrud, E. P.; Connoliy, M. J. J. Chromatogr. 1982, 239, 397-410. (11L) Grinsrud, E. P.; Knighton, W. B. Anal. Chem. 1982, 54, 565-70. (12L) Hu, 2.; Chen, T.; Wu, H. Youji Huazue 1982, 2 , 139-41. (13L) Pacholec, F.; Poole, C. F. Anal. Chem. 1982, 54, 1019-21. (14L) . . P o o h C. F. J. Hlgh Resolut. Chromatogr. Chromatogr. Commun. 1982, 5(a), 454-71. (15L) Pooie, C. F.; Zlatkis, A. Electron Capture; Theory fract. Chromatogr., J. Chromatogr. Library 1981, 20, 13-26. (16L) Popp, P.; Lesnhardt, J.; Oppermann, G. ZfI-Mltt. 1981, 43a, 127-42. (17L) Shrnldel, E. B.; Rotin, V. A.; Bodrlna, D. E. Khim. from-st., Ser.: Autom. Khlm. Proizvod. 1982, (I), 35-8. (18L) Siu, K. W.; Aue, W. A. Mikrochlm. Acta. 1983, l(5-6), 419-30. (19L) Takeuchl, M. 8unseki Kagaku 1982, 37(9), T70-T74. (20L) Toyoura, Y. Kogai to Taisaku 1981, 77(9), 875-81. (21L) Wells, G.; Simon, R. J. High Resolut. Chromatogr. Chromatogr. Commun. 1983, 6 , 427-30. (22L) Wizner, M. A.; Slnghawangcha, S.;Barkley. R. M.; Sievers, R. E. J. Chromatogr. 1982, 239, 145-57. (23L) WoJnarovits, L.; Foldlak, G. J. Chromatogr. 1982, 234, 451-3. Flame Photornetrlc Detectors (FPD) (IM) Cardweil, T. J.; Marriott, P. J. J. Chrom. Sci. 1982, 20, 83-90. (2M) Dressler, M. J. Chromatogr. 1983, 262, 77-84. (3M) Jackson, J. A,; Blair, W. R.; Brinckman, F. E.; Iverson, W. P. Environ. sci. Technol. 1982, 16(2), 110-19. (4M) Sevcik, J. Int. J. Envlron. Anal. Chem. 1983, 13(2). 115-28. (5M) Sotnlkov, E. E.; Babanov, N. I . U.S.S.R. Patent 1000905, 28 Feb. 1983. (6M) Thomas, L. C.; Adams, A. K. Anal. Chem. 1982, 5 4 , 2597-99. Photolonlzatlon Detectors (PID) (1N) Drlscoll, J. D. J. Chromafogr. Scl. 1982, 20, 91-94. (2N) Freedman, A. N. J. Chromatogr. 1982, 236, 11-15. (3N) Kapila, S.; Bornhop, D. J.; Manahan, S. E.; Nickell, 0. L. J. ChromatOgr. 1983, 259, 205-210. (4N) Yancey, J. A. Adv. Instrum. 1982, 37(2), 547-57. Thermionic lonlzatlon Detectors (TID) (10) Chang, D.; Wang, X.; LI, A.; Gong, P.; Lin, 8. Kexue Tongbao 1982, 27(22), 1373-5. (20) Devyatykh, 0. G.; Krylov. V. A.; Makarov, V. E.; Utorov, B. G. Zh. Anal. Khim. 1982. 37(5), 887-9. (30) Patterson, P. L.; Gatten, R. A.; Ontiveros, C. J. Chromatogr. Scl. 1982, ' 20, 97-102. (40) Slstl, G.; Verga, G. EP 66735, 15 Dec. 1982. (50) Thompson, D. C.; Stoicheff, B. P. Rev. Sci. Insfrum. 1982, 53(6), 822-8. (60) Zhang, D.; Lln, B. Kexue rongbao 1982, 27(24), 1500-3. Infrared ( I R ) end Fourier-Transform Infrared (FTIR) Detector (1P) Foster, 8. D.; Walker, R. F. Analyst(London) 1982, 707(1279), 1181-9. (2P) Garlock, S. E.; Adams, G. E.; Smith, S . L. Am. Lab. 1982, 74(12), 48-55. (3P) Garrlson, A. A.; Hembree, D. M., Jr.; Yokley, R. A.; Crocombe, R. A.; Mamantov, G.; Wehry, E. L. froc. SPIE-Int. SOC.Opt. Eng. 1981, 289, 150-3. (4P) Grifflths. P. R.; deHaseth, J. A,, Azanaga, L. V. Anal. Chem. 1983, 55, 1361A-1387A. (5P) Gurka, D. F.; Betowski, L. D. Anal. Chem. 1982, 54(11), 1819-24. (6P) Gurka, D.F.; Laska, P. R.; Titus, R. J. Chromatogr. Sci. 1982, 20(4), 145-54. (7P) Hangac, G.; Hohne, B. A.; Isenhour, T. L. J. Chromatogr. Sci. 1983, 21, 241-45. (8P) Isenhour, T. L.; Marshall, J. C. Anal. Chem. Symp. Ser. 1983, 14, 1-27. (9P) Jalsovszky, G.; Holly, S.; Imre, L. Magy. Kem. Foly. W82, 88(5), 197-202. (IOP) Kalasinsky, K. S . J. Chromatogr. Scl. 1983, 21, 246-53. ( l i p ) Krlshman, K.; Brown, R. H., Hili, S.L.; Slmonoff, S. C.; Olson, M. L.; Kuehl, D. Int. Lab. 1982, 17(4), 66, 68-70, 72, 74-5. (12P) Kuehl, D. froc. SHE-Int. SOC.Opt. Eng. 1981, 289, 140-2. (13P) Lam, R. B.; Sparks, D. T.; Isenhour, T. L. Anal. Chem. 1982, 5 4 , 1927-31. (14P) Mallssa, H., Jr. Fresenlus' Z . Anal. Chem. 1982, 373(2), 116-20. (15P) Malissa, H. Oesterr. Chem. 2. 1983, 84(1), 1-6. IMP) McDonald, J. T.; Kalasinsky, V. F. Proc. SPIE-Int. SOC. Opt. Eng. ' 1081, 269, 154-5. (17P) Owens, P. M.; Lam, R. B.; Isenhour, T. L. Anal. Chem. lg82, 5 4 , 2344-47 -_. . .. . (18P) Rosslter, V. Am. Lab. 1982, 74(6), 71-2, 74, 78-9. (19P) Rosslter, V. Am. Lab. 1982, 74(2), 144, 146-52. (20P) Seelemann, R. TrAC, Trends Anal. Chem. 1982, 1(14), 333-9. (21P) Shafer, K. H.; Hayes, T. L.; Tabor, J. E. R o c . SHE-Int. Soc. Opt. Eng. W81, 289, 160-4. (22P) Smlth, S. L.; Garlock, S.E.; Adams, G. E. Appl. Spectrosc. 1983, 37(2), 192-6. (23P) Sparks, D. T.; Lam, R. B.; Isenhour, T. L. Anal. Chem. 1982, 5 4 , 1922-26. (24P) Wilkens, C. L.; Giss, G. N.; Whlte, R. L.; Brissey, G. M.; Onylrluka, E. C. . Anal. Chem. 1982, 5 4 , 2260-2264. (25P) Wllllams, S. S.; Lam, R. B.; Sparks, D. T.; Isenhour, T. L.; Hass, J. R. Anal. Chim. Acta 1982, 738, 1-10.
196R
ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
(26P) Wltek, H.; Knecht, J. Labor Praxis 1981, 5(12), 1054-8. Spectrometric Detectors (10) Baim, M. A.; Hili, H. H., Jr. J. High Resolut. Chromatogr. and Chromatogr. Communlc. W83, 6, 4-10. (2Q) Balm, M. A.; Eatherton, R. L.; Hill, H. H., Jr. Anal. Chem. 1983, 55, 1761-66. (3Q) Balm, M. A., Hili, H. H., Jr. Anal. Chem. 1982, 5 4 , 38-43. (4Q) Borman, S. A. Anal. Chem. 1983, 55, 726A-30A. (5Q) Cerbus, C. S.;Gluck, S. J. Spectrochim. Acta, Part8 1983, 388(1-2), 387-97. (6Q) Chevrier, G.; Hanai, T.; Tran, K. C.; Hubert, J. Can. J. Chem. 1982, 60(7), 898-903. (7Q) Conrad, V. B.; Carter, W. J.; Wehry, E. L.; Mamontou, G. Anal. Chem. 1983, 55, 1340-4. (8Q) Dumarey, R.; Dams, R.; Sandra, P. J. High Resolut. Chromatogr. Chromatogr. Communic. 1982, 5 , 687-9. (9Q) Ebdon, L.; Ward, R. W.; Leathard, D. A. Analyst (London) 1982, 107(1271). 129-43. (lOQ) Eckhoff, M. A,; McCarthy, J. P.; Caruso, J. A. Anal. Chem. 1982, 5 4 , 165-8. (1lQ) Eckhoff, M. A.; Ridgway, T. H.; Carueo, J. A. Anal. Chem. 1983, 55, 1004-9. (12Q) Frlegleri, R.; Fenaroli, R. Cron. Chim. 1982, 70, 3-19. (13Q) Fuwa, K.; Haraguchi, H.; Morita, M.; VanLoon, J. C. Bunko Kenkyu 1982, 37(5), 289-305. (142) Genna, J. L.; McAnlnch, W. D.; Reich, R. A. J. Chromatogr. 1982, 238, 103-112. (15Q) Green, R. Anal. Chem. 1983, 55, 20A-32A. (I6Q) Hagen, D. F.; Belisle, J.; Marheuka, J. S. Spectrochim. Acta, Part8 1983, 388(1-2), 377-85. (17Q) Hayes, J. M.; Small, G. J. Anal. Chem. 1982, 54, 1204-6. (I8Q) Kashihlra, N.; Makino, K.; Klrita, K.; Watanabe, Y. J. Chromatogr. 1982, 239, 617-624. ( l e a ) Mach, M. H.; Sutton, D. G.; Meizer, J. E. Appi. Spectrosc. 1982, 36(5), 597-8. (20Q) Muillgan, K. J.; Zerezhgl, M.; Caruso, J. A. Spectrochim. Acta, Part 8 1983, 368(1-2), 369-75. (21Q) Ohls, K.; Sommer, D.D e v . At. Plasma Spectrochem. Anal., froc. Int. Winter Conf. 1980, 321-36. (22Q) Paril, J. D.; Paul, D. W.; Green, R. B. Anal. Chem. 1982, 5 4 , 1967-72. (23Q) Qlng-Yu, 0.; Guo-Chuen, Wi; Ke-Wei, 2.; Wei-Lu, Y. Spectrochlm. Acta, Part 8 lg83, 388(1-2), 419-25. (24Q) Rlsby, T. H.; Tairnl, Y. CRC Crit. Rev. Anal. Chem. 1983, 14(3), 231-65.. (25Q) Rudnevskli, N. K.; Demarln, V. T.; Sklemina, L. V. Zh. frikl. Spektrosk. 1983, 38(1), 61-76. (26Q) Steiglitz, L.; Zwick, G. Comrn. Eur. Comrnunitles, [Rep.] 1982, Anal. Org. Micropollut. Water, 105-12. (27Q) Tanabe, K.; Haraguchi, H.; Fuwa, K., Spectrochim. Acta, Part 8 W81, 368171. 633-9. ---\-,* --- - (28Q) Uden, P. C. Dev. At. Plasma Spectrochem. Anal. R o c . Int. Winter Conf. 1980, 302-20. (29Q) VanLoon, J. 6. Can. J. Spectrosc. 1981, 26(4), 22A-32A. (30Q) Yamada, M.; Ishiwada, A.; Hobo, T.; Suzuki, S.;Araki, S. J. Chromatogr. 1982, 238, 347-356. (31Q) Zharov, V. P.; Montanari, S.G.; Letokhov, V. S . Laser Chem. 1983, 1(3), 163-76. '
Ionlzatlon Detectors (1R) Fuchs, H. Rev. Tec. Fac. Ing., Univ. Zulia 1980, 3(2), 155-63. (2R) Osman, M. A,; HID, H. H., Jr. Chromatogr. 1983, 264, 149-53. (3R) Osman, M. A.; Hill, H. H., Jr. Anal. Chem. IS82, 5 4 , 1425-28. (4R) Popp, P.; Arnold, G.; Opperman, G. Isotopenpraxls 1983, 79(5), 156-7. (5R) Rice, 0. W.; Richard, J. J.; D'Silva, A. P.; Fassel, V. A. Anal. Chim. Acta 1962, 742, 47-54. (6R) Rlce, 0. W.; Richard, J. J.; D'Silva, A. P., Fassel, V. A. J. Assoc. Off. Anal. Chem. l W 2 , 65(1), 14-19. (7R) Schneider, W.; Frohne, J.; Bruderreck, H. J. Chromatogr. 1982, 245, 71-83. (8R) Sotnikov, E.; Voikov, S . A. Zh. Anal. Khlm. 1981, 36(12), 2304-7. Electrochemical Detectors
(IS)Gluck, S . J. Chromatogr. Scl. 1982, 20(3), 103-8. (2s) Kirshen, N. A. V I A , Varian Instrum. Appl. 1982, 16(2), 6-7. (3s) Rudenko. B. A,: Gorvachev, N. S.:Gavrilov, V. V. Zh. Anal. Khim. ' 1982, 37(3), 544-7. . (4s) Yoshlda, H.; Okuno, K.; Maruse, Y. J. Nucl. Sci. Technol. 1982, 79(2), 578-86. Mass Spectrometry Detectors (1T) (2T) (3T) (4T)
Dlxon, D. Lab. fract. 1983, 32(3), 63, 65. Heppner, R. A. Anal. Chem. 1983, 55, 2170-4. Vogt. J.; Kuederli, F. K. GITFachz. Lab. 1983, 27(2), 116-19. White, R. L.; Wilkins, C. L. Anal. Chem. 1982, 5 4 , 2443-47.
Comblnation Detectors
(1U) Borrnan, S. A. Anal. Chem. 1982, 5 4 , 901A-905A. (2U) Cox, R. D.; Earp, F. R. Anal. Chem. 1982, 5 4 , 2265-70. (3UI Crawford. R. W.: Hirschfeld, T.; Sanborn, R. H.; Wong, C. M. Anal. ' Chem. 1982, 54, 817-20. (4U) Fuchsbichler, G.; BIOS, G. Landwirtsch Forsch., Sonderh. 1981, 38, 774-80.
GAS CHROMATOGRAPHY (5U) Gagllardl, P.; Verga, G. R. Chem. Foods Beverages: Recent Dev. 1982, 49-72. (6U) Klngsley, B. A.; Gin, C.; Coulson, D. M.; Thomas, R. F. Water Chlorination: Environ. Impact Health Eff. 1983, 4 , 596-608. (7U) Kruii, I. S.; Swartz, M.; Hilliard, R.; Xie, K.-H. J. Chromatogr. 1983, 260, 347-62. (8U) Lopez-Avila, V.; Northcutt, R. J . High Resoluf Chromafogr . Chroma togr. Communic. 1982, 5, 67-74. (9U) Malissa, H., Jr. Fresenius’ 2.Anal. Chem. 1982, 311(2), 123-4. (IOU) Nutmagul, W.; Cronn, D. R.; Hill, H. H., Jr. Anal. Chem. 1983, 55, 2 160-64. (1lU) Possanzini, M.; Ciccioli, P.; Brancaieonl, E.; Tappa, R.; Brachetti, A. Comm. Eur. Communltles, [Rep.] 1982, Phys.-Chem. Behav. Atmos. Pollut., 76-81. (12U) Rudolph, J.; Jebsen, C. Int. J . Envlron. Anal. Chem. 1983, 13(2), 129-39. (13U) Sandra, P.; Verzele, M.; Vanluchene, E. J . High Resoiuf. Chromatogr. Chromatogr . Communic. 1983, 6 , 504-6. (14U) Sass, S.; Steger, R. J. J . Chromatogr. 1982, 238, 121-32. (15U) Stafford, A. E.; Corse. J. J . Chromatogr. 1982, 247, 176-9. (16U) Towns, B. D.; Driscoll, J. N. Am. Lab. 1982, 14(7), 56, 59-62. (17U) Vogt, C. R.; Kapila, S., Manahan, S. E. Int. J . Envlron. Anal. Chem. 1982, 12(1), 27-40.
.
-
OTHER TECHNIQUES
Physical-Analytlcal Measurements (1V) Acree, W. E., Jr. J. fhys. Chem. 1982, 66(8), 1461-5. (2V) AI-Dhahir, A. A. K.; Swan, I . M. J . Indlan Chem. SOC. 1982, 59(5), 645-53. (3V) Alessl, P.; Giadrlnl, D.; Torriano, G.; Volpe, S. Ind. Vernice 1982, 36(11), 12-19. (4V) Alessl, P.; Kiklc. I.; Alessandrini, A.; Fermeglia, M. J . Chem. Eng . Data i982, 27(4). 445-8. (5V) Alessi, P.; Kikic, I.; Alessadrinl, A.; Orlandinl, V. M. Chem. Eng. Commun. 1982, 16(1-6), 377-82. (6V) Alessi, P.; Klkic, I.; Nonino, C.; Vlsalberghl, M. 0. J . Chem. Eng. Data 1982, 27(4), 448-50. (7V) Alvarez, R.; Domlnguez, J. M.; Coca, J. Chromatographla 1983, 17(3), 166-8. (6V) Bogllio, V. I.; Filonenko, G. V. Deposited Doc. 1981, SPSTL 916 KhpD81, 91-7. (9V) Castells, R. C.; Aranclbia, E. L.; Nardillo, A. M. J . Colloid Interface Scl. 1982. 90(2\. 532-5. (1OV) dasteils,’ R. C.; Aranclbia, E. L.; Nardlllo. A. M. An.-CIDEPINT 1982, 215-26. (11V) Courval, G. J.; Gray, D. 0. foiymer 1983, 24(3), 323-8. (12V) Dmitryuk, 0. G.; Auots, A. Lafv. PSRZinat. Akad. Vestis, Kim. Ser. 1982, (5), 585-9. (13V) Dolezal, 6.; Holub, R. Chem. Listy 1982, 76(4), 362-74. (14V) Gavrilova, T. 6.; Roshchina, T. M. I z v . Khim. 1982, 15(1), 135-40. (15V) Grumadas, A. J.; Poshkus, D. P.; Kiselev, A. C. J . Chem. Soc., Faraday Trans. 2 1982, 78(12), 2013-23. ( l e v ) Habboush, A. E.; Nassory, N. S. Iraql J . Sci. 1981, 23(3), 362-77. (17V) Huang, J. C.; Madey, R. J . Chromatogr. Scl. 1982, 20(5), 218-20. (18V) Janlnl, 0.M.; Ubeld, M. T. J . Chromatogr. 1982, 236, 329-337. (19V) Kaliszan, R.; Holtje, H.-D. J . Chromafogr. 1982, 234, 303-11. (2OV) Karaiskakls, G.; Katsanos, N. A.; Nlotis, A. J . Chromatogr. 1982, 245(1), 21-9. (21V) Karaiskakis, G.; Lycourghiotis, A.; Katsanos, N. A. Chromatographia 1982, 15(6), 351-4. (22V) Kuchhal, R. K.; Malllk. K. L. J . Chromafogr. 1982, 235, 109-117. (23V) Kullkov, V. I.; Kovalevskaya, V. A.; Markevlch, S. V. Vestsi Akad. Navuk BSSR, Ser. Khim Navuk 1982, (4), 109-11. (24V) Langer, S. H.; Sheehan, R. J.; Huang, J. C. J. fhys. Chem. 1982, 86(23), 4605-18. (25V) Leca, M. Rev. Roum. Chlm. 1982, 27(8), 987-92. (26V) Lln, P. J.; Parcher, J. F. J . Chromatogr. Sci. 1982, 20(1), 33-8. (27V) Mason, R. S.; Clifford, A. A.; Gray, P.; Waddlcor, J. I.froc. Symp. Thermophys. Prop. 1982, 8(1), 281-8. (28V) Meyer, E. G. Am. Lab 1982, 14(10), 44, 46-6, 50, 52-3. (29V) Meyer, E. F.; Ellefson, J. J . Chromatogr. 1982, 249, 239-44. (30V) Meyer, E. F.; Zlalinski, W. M. J . Chem. Thermodn. 1982, 14(5), 403-7. (31V) Nabivach, U. M.; Klrllenko, A. V. Vopr. Khim. Tekhnol. 1980, 58, 137-43. (32V) Ohta, K.; Smith, B. W.; Suzukl, M.; Wlnefordner, J. D. Spectrochlm. Acta, Part B 1982, 378 (4), 343-7. (33V) Prlboth, I.; Van Pham, S.; Engewald, W.; Qultzsch, K. Chem. Tech (Llepzig)1982. 34(12), 649-51. (34V) Schrljver, J.; Ammerdorffer, J. L.; German, A. L. J . foiym. Scl., f o iym. Chem. Ed. 1982, 20(9), 2693-703. (35V) Tadzhleva, N. Kh.; Prokop’eva, M. F. Deposited Doc. 1981, SPSTL 863 Khp-081, 7 pp. (36V) Thomas, E. R.; Newman, B. A.; Long. T. C.; Wood, D. A.; Eckert, C. A. J. Chem. Eng. Data 1982, 27(4), 399-405. (37V) Uchlzono, Y.; Kal, M.; Tashima, Y.; Arai, Y. Kyushu Daigaku, Kogaku Shuko 1982. 55f3). 213-19. (38V) Valko, K.; Lopata, A. J. Chromatogr. 1982, 242, 77-90. lnorsanlc GC (IW) Baechmann, K. Talanta 1982, 29(1), 1-25. (2W) Baudo, R. Acqua Aria 1982, (7), 703-15. (3W) Bendlg, U.; Stenner, H.; Kettrup, A. Fresenius’ 2 . Anal. Chem. 1981, 309(5), 370-2.
(4W) Chovancova, J.; Krupclk, J.; Rattay, V.; Garaj, J. J . Chromatogr. 1983, 256, 465-6. (5W) Crompton, T. R. “Gas Chromatography of Organometallic Compounds”; Plenum Press: New York, 1982. (6W) De Jongke, W.; Adams, F Fresenius’ 2.Anal. Chem. 1983, 314(6), 552-4. (7W) Egorova, S. A.; Rakhouskaya, S. M.; Bolotlna, N. E.; Tugushev, R. E.; Arbuzova, T. K. Kolloidn. Zh. 1983, 45(2), 321-3. (8W) Estes, S. A.; Uden, P. C. Barnes, R. M. J . Chromatogr. 1982, 239, 181-9. (9W) Hartmetz, G.; Scollany, G.; Meierer, H.; Meyer, A.; Neeb, R. Fresenius’ 2.Anal. Chem. 1982, 313(4), 309-12. (low) Hoyes, M.; Vandegans, J.; Hartman, J. P.; Leemans, J. P. Congr. FATIPEC 1982, 16th (Vol. 3), 313-30. (11W) Jover, 6.; Juhasz, J.; Szabo, 2. Magy, Kem. Foly. 1982, 88(11), 492-6. (12W) Klto, A.; Nakane, M.; Miyake, Y. Nippon Kagaku Kaishi 1982, (4), 620-6. (13W) Kotsev, N.; Shopov, D. I z v . Khlm. 1982, 15(1), 61-6. (14W) Kuwamoto, T.; Matsubana, N., Bunseki 1982, (5), 310-18. (15W) Marrlott, P. J.; Eglinton, G., J. Chromafogr. 1982, 249, 311-21. (16W) Marriott, P. J.; Gill, J. P.; Egllnton, G. J . Chromatogr. 1982, 236, 395-401. (17W) Marriott, P. J.; Gill, J. P.; Eglington, G. J. Chromatogr. 1982, 249, 291-310. (l8W) Meyer, A.; Neeb, R. Fresenius’ 2. Anal. Chem. 1982, 313(3), 221-4. (19W) Patnl, P. M.; Sande, S. P. Chem. Era 1982, 18(1), 1-5. (20W) Pllll, S.; Maltra, A. M. J . Chromatogr. 1983, 254, 133-41. (21W) Schurig, V.; Weber, R. J . Chromatogr. 1981, 217, 51-70. (22W) Sievers, R. E.; Brooks, K. C. Inf. J. Mass Spectrom. Ion fhys. 1983, 47, 527-30. (23W) Slu, K. W. M.; Fraser, M. E.; Berman, S. S. J . Chromatogr. 1983. 256(3), 455-9. (24W) Steldl, G.; Baechmann, K.; Delnstbach, F. Fresenius’, Z . , Anal. Chem. 1983, 314(2), 146-51. (25W) Wang, X.; Wu, P.; Xin, X.; Dai, A. Huaxue Xuebao 1983, 41(1), 48-55. (26W) Xin, X.; Wang, X.; Zhang, X.; Dai, A. Huaxue Xuebao 1982, 40(12), 1111-22. (27W) Yanovskli, M. I.; Berman, A. D. Zh. Vses. Khim. 0 - V a . 1983, 28(1), 67-90. Novel Appllcatlons (IX) Bellabes, R.; Granger, R.; Vergnaud, J. M. Sep. Scl. Technoi. 1982, 17(9), 1179-82. (2X) Duarte, P. E.; McCoy, B. J. Sep. Sci. Techno/. 1982, 17(7), 879-98. (3X) Igarashi, A.; Ogino, Y. Appl. Catal. 1982, 2(6), 339-45. (4X) Katsanos, N. A. J . Chem. Soc., Faraday Trans. 1 1982, 78(4), 1051-63. (5X) Katsanos, N. A.; Karaiskakis, G. J . Chromatogr. 1982, 237(1), 1-14. (ex) Katsanos, N. A.; Karalskakls, G.; Vattis, D.; Lycourghlotis, A. Chromatographia 1981, 14(12), 695-8. (7X) Luebke, M.; Severin, D.; Schulz, H.; Janssen, 0. Ber.-Dtsch. Ges. Mineraioeiwiss . Kohiechem. 1982, 241-02. (6X) Mlkaya, A. I.; Smetmanln, V. I.; Zaikln, V. G. I z v . Akad. Nauk SSSR, Ser. Khim. 1982, (IO), 2270-7. (9X) Notheisz, F.; Zsigmond, A. G.; Bartok, M. J. Chromatogr. 1982, 241, 101-2. QUALITATIVE AND QUANTITATIVE ANALYSIS Qualltatlve Analysls (IY) Anderson, W. H.; Stafford, D. T. J. High Resolut. Chromatogr. Chromatogr. Commun. 1983, 6 , 247. (2Y) Ardrey, R. E.; Moffat, A. C. J . Chromatogr. 1981, 220, 195. (3Y) Bertsch, W.; Mayfield, H.; Thomason, M. M. froc. Int. Symp . Capillary Chromatogr., 4th 1981, 313. (4Y) Bredael, P. J. High Resoluf. Chromatogr. Chromatogr. Commun. 1982, 5, 325. (5Y) Campbell, J. A.; Grlmsrud, E. P. J . Chromatogr. 1982, 243, 1. (6Y) Dement’eva, N. N.; Zavrazhnaya, T. A.; Potapova, V. N. Farmafsiya 1982, 31, 37. (7Y) Driscoll, J. N. J . Chromatogr. Sci. 1982, 2 0 , 91. (8Y) Evans, M. B. Chromafographie 1982, 15, 355. (9Y) Fish, R. H.; Newton, A. S.; Babbitt, P. C. Fuel 1982, 61, 227. (1OY) Foster, D. 0.; Zinkel, D. F. J . Chromatogr. 1982, 248, 89. ( I l Y ) Gajewski, E.; Dlzdaroglu, M.; Simlc, M. G. J . Chromatogr. 1982, 249, 41. (12Y) Goebel, K. J. J . Chromatogr. 1982, 235, 119. (13Y) Golovnya, R. V.; Garbuzoz, V. G.; Aerov, A. F. Izu, Akad. Nauk SSSR, Ser. Khim. 1981, 2284. (14Y) Gurka, D. F.; Laska, P. R.; Titus, R. J . Chromatogr. Sci. 1982, 2 0 , 145. (15Y) Hangac, G.; Hohne, B. A.; Isenhour, T. L. J . Chromatogr. Sci. 1983, 21, 241. (l6Y) Holland, P. T.; McGhle, T. K.; McGaveston, D. A. festlc. Chem.: Hum. Welfare Environ., R o c . Int. Congr. fesfic. Chem., 5th 1982, 4 , 73. (17Y) Hsu, F. S.; Good,E. W.; Parrlsh, M. E.; Crews, T. D. J . HighResolut. Chromatogr. Chromatogr. Commun. 1982, 5, 648. (18Y) Humphrey, A. M. Anal. R o c . 1982, 19, 197. (l9Y) Jaworskl, M. frzem. Chem. 1982, 61, 334. (20Y) Jelium. E.; Bjoernson, I.; Nesbakken, R.; Johansson, E.; Wold, S. J. Chromatogr. 1981, 217, 231. (21Y) Johansen, N. G.; Ettre, L. S . Chromatographia 1982, 15, 625. ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
197R
GAS CHROMATOGRAPHY (22Y) Knoeppel, H.; De Bortoli, M.; Peil, A.; Schauenburg, H.; Vissers, H. Comm. Eur. Communltles EUR 1982, 7624, Phys.-Chem. Behav. Atmos. Pollut. 1982, 99. (23Y) Knoeppel, H.; De Bortoli, M.; Peil, A,; Schauenburg. H.; Vlssers, H. Comm. Eur. Communltles EUR 1982, 7623, Anal. Org. Micropollut. Water 1982, 133. (24Y) Komarek, K.; Capek, A.; Churacek, J. Sb. Ved. Pr., Vys. Sk. Chemickotechnol. Pardubice 1981, 4 4 , 47. (25Y) Komarek, K.; Borecky, K.; Dadak, B.; Churacek, J. Sb. Ved. Pr., Vys Sk. Chemickotechnol. Pardubice 1981, 4 4 , 65. (26Y) Larson, P.; Stark, T.; Dandeneau, R. Proc. Int. Symp. Capillsty Chromatogr. 4th 1981, 727. (27Y) Macek, J.; Nabivach, V. M.; Buryan, P.; Sindler, S. J. Chromatogr. 1982, 234, 285. (28Y) MacFle, H. J. H. Anal. Proc. 1982, 19, 529. (29Y) Morgan, S. L. Org. Coat. Plast. Chem. 1981, 4 4 , 600. (30Y) Novak, J.; Vejrosta, J.; Roth, M.; Janak, J. Adv. Chromatogr. 1980, 15. ., 209. -.. (31Y) Novotny, M.; Merll, F.; Wlesler. D.; Fend, M.; Saeed, T. J. Chromatogr. 1982, 238, 141. (32Y) Parees. D. M.; Kamzelskl, A. 2. J. Chromatogr. Sci. 1982, 2 0 , 441. (33Y) Picer, M. Comm. Eur. Cornmunlties, EUR 1982, 7623, Anal. Org. Micropollut. Water 1982, 48. (34Y) Roth, M.; Novak, J. J. Chromatogr. 1982, 234, 337. (35Y) Saura Calixto, F.; Garcia Raso, A.; Bermejo, J. An. Qulm., Ser. C 1981, 7 7 , 178. (36Y) Shankles, E.; Weinberg, S.B.; Dal Cortlvo, L. A. J. Anal. Toxicol. 1982, 6, 241. (37Y) Sldorov, R. I. Zh. Fir. Khim 1982, 5 6 , 1057. (38Y) Stead, A. H.; Gill, R.; Evans, A. T.; Moffat, A. C. J. Chromatogr. 1982, 234, 277. (39Y) Tanaka, K.; Hine, D. G. J. Chromatogr. 1982, 239, 301. (40Y) Vassllaros, D. L.; Kang, R. C.; Later, D. W.; Lee, M. L. J. Chromatogr. 1982, 252, 1. (41Y) Vrbanac. J. J.; Sweeley, C. C.; Pinkston, J. D. Biomed. Mass Spectrom. 1983, 10, 155. (42Y) White, C. M.; Li, N. C. Anal. Chem. 1982, 5 4 , 1564. (43Y) Wlnskowskl, J. J . Chromatographia 1983, 17, 160. (44Y) Wlzner, M. A.; Slnghawangcha, S.; Barkley, R. M.; Sievers, R. E. J. Chromatogr. 1982, 239, 145. (45Y) Zygmunt, B.; Staszewski, R. Chem. Anal. 1981, 2 6 , 109.
.
Quantltatlwe Analysls (12) Birke, H. GIT Fachz. Lab. 1983, 2 5 , 28. (22) Edwards, T. R. Anal. Chem. 1982, 54, 1519. (32) Eichelberger, J. W.; Kerns, E. H.; Olynyk. P.; Budde, W. L. Anal. Chem. 1983, 55, 1471. (42) Ettre, L. S. Chromatogr. News/. 1981, 9 , 46. (52) Excoffler, J. L.; Gulochon, 0. Chromatographia 1982, 15, 543. (62) Excoffier, J. L.; Jaulmes, A.; Vldal-Madjar, C.; Guichon, G. Anal. Chem. 1982, 54, 1941. (72) Friedli, F. J. High. Resolut. Chromatogr. Chromatogr. Commun. 1981, 4,495. (82) Grob, K., Jr.; Mueller, R. J. Chromatogr. 1982, 244, 185. (92) Gulllemln, C. L. J. Chromatogr. 1982, 239, 363. (102) Hall, G.; Winterlln, W. Am. Lab. 1983, 15, 84. (112) Henneberg, D. Commun. Eur. Communltles, EUR 1982, 7623, Anal. Org. Mlcropoilut. Water 1982, 219. (122) Hlnshaw, J. V., Jr.; Yang, F. J. J. High Resolut. Chromatogr. Chromatogr. Commun. 1983, 6 , 554. (132) Hinshaw, J. V., Jr.; Felnstein, P. L. Am. Lab. 1983, 15, 116. (142) Jones, D.; Curvaii, M.; Abrahamsson, L.; Kazeml-Vaia, E.; Enzell, C. Blomed. Mass Spectrom. 1982, 9 , 539. (152) Kaiser, R. E.; Rieder, R. I.Proc. Int. Symp. Capillary Chromatogr., 4th 1981, 885. (162) Kalmanovskii, V. I.Zh. Anal. Khim. 1982, 3 7 , 1309. (172) Knoll, J. E.; Mldgett, M. R. J. Chromatogr. Sci. 1982, 2 0 , 221. (182) Lam, R. B.; Sparks, D. T.; Isenhour, T. L. Anal. Chem. 1982, 5 4 , 1927. (192) Lundeen, J. T. 1982, Avall. Univ. Mlcrofllms Int.. Order No. DA8300990. From Diss. Abstr. Int. B 1983, 43, 2536. (202) Mllllngton, D. S. Commun. Eur. Communities 1982, 7137, Appl. Mass Spectrom. Trace Anal. 1982, 189. (212) Novak, J. Adv. Chromatogr. 1983, 2 1 , 303. (222) Purcell, J. E. Chromatographla 1982, 15. 546. (232) Raphaellan. L. A. Prepr. Pap.-Am. Chem. SOC.,Dlv, Fuel Chem. 1981, 2 6 , 77. (242) Rhodes, G.; Opsai. R. B.; Meek, J. T.; Rellly, J. P. Anal. Chem. 1883, 55, 280. (252) Richardson, P. T.; De Haseth, J. A. Comput. Appl. Lab. 1983, 1 , 64. (262) Roeraade, J.; Blomberg. S. Chromatographla 1983. 17, 387. (272) Rosenbaum, M.; Hancll, V.; Komers, R. J. Chromatogr. 1982, 246, 1. (282) Sauter, A. D.; Mills, P. E.; Fltch, W. L.; Dyer, R. J . High Resolut. Chromatogr. Chromatogr. Commun. 1982, 5 , 27. (292) Sharaf, M. A.; Kowalski, 8. R. Anal. Chem. 1982, 5 4 , 1291. (302) Takayama, Y. J . High Resolut. Chromatogr. Chromatogr. Commun. 1982, 5,211. (312) Wagener, J. B.; Buys, T. S. Comput. Appl. Lab 1983, 1, 210. (322) Walling, P. L.; Gentille, T. E.; Gudat, A. E. Am. Lab 1982, 14, 22. (332) Wang, F. S.;Shanfield, H.; Zlatkis, A. J. High Resolut. Chromatogr. Chromatogr. Commun. 1982, 5 , 562. (342) Wetzel, E.; Kuster, T. J. Chromatogr. 1983, 268, 177. (352) Yang, F. J. J. High Chromatogr. Chromatogr. Commun. 1983, 6 , 440. (362) Zlegler, E.; Weimann, B.; Wronka, In.; Schamburg, G.; Haeuslg, U. Anal. Chim. Acta 1983, 147. 91.
198R
ANALYTICAL CHEMISTRY, VOL. 56, NO. 5, APRIL 1984
(372) Zlatkls, A.; Wang, F. S.; Shanfleld, H. Anal. Chem. 1983, 5 5 , 1848. METHODOLOGY
Instrurnentatlon (IAA) Abbott, D. J. J. Chromatogr. Sci. 1983, 2 1 , 425. (2AA) Ceballo, C.; Murgia, E. Rev. Tec. INTEVEP 1981, 1, 99. (3AA) Dennis, W. H. Anal. Instrum. 1982, 20,43. (4AA) Heisz, 0. GIT Fachz. Lab. 1982, 2 6 , 667. (5AA) Hollis, M. G.; Grant, D. W. Comput. Appl. Lab. 1983, 7 , 68. (BAA) Hurt, S. G.; Welton, B. Am. Lab. 1983, 15, 89. (7AA) Kapila, S.; Bornhop, D. J.; Manahan, S. E.; Nlckell, G. L. J. Chromatogr. 1983, 259, 205. (BAA) Kingsley, B. A.; Gin, C.; Coulson, D. M.; Thomas, R. F. Water Chlorination: Environ. Impact Health Eff, 1983, 4 , 593. (9AA) Kuehl, D. Proc. SPIE-Int. Soc. Opt. Eng. 1981, 289. (IOAA) Nutmagul, W.; Cronn, D. R.; Hill, H. H., Jr. Anal. Chem. 1983, 5 5 , 2160. (11AA) Oba, K.; Rehak, P.; Smlth, S. D. Eftore Majorana Int. Sci. Ser.: Phys. Sci. 1983, 14, 121. (12AA) Rossiter, V. Am. Lab. 1982, 1 4 , 71. (13AA) Shafer, K. H.; Hayes, T. L.; Tabor, J. E. Proc. SPIE-lnt. SOC.Opt. Eng. 1981, 289, 160. (14AA) Sotnikov, E. E.; Babanov, N. I. Otkrytiya, Izobret., Prom. Obraztsy, Tovarnye Znakl 1983, 8 , 179. (15AA) Tekler, V.; Takacs, J. Magy. Kem. Foly. 1982, 8 8 , 459. (16AA) Woodruff, T. A. US. Patent 4316381, 23 Feb. 1982, Appl. 167856, 14 July 1980. Pyrolysls (lBB) Dimov, N.; Mllina, R. Vysokomol. Soedln., Ser. A 1981, 2 3 , 2486. (288) Dimov, N.; Milina, R. J. Anal. Appl. Pyrolysis 1983, 4 , 265. (3BB) Dobal, V.; Sebesta, P.; Kas, V. Therm. Anal., Proc. Int. Conf., 7th 1982, 2 , 1254. (488) Ericsson, I. Proc.-Int. Kohlenwlss. Tag. 1981, 601. (588) Gassiott-Matas, M.; Alcanlz-Baldellou, J. M.; Andress-Canadeil, J. J. Anal. Appl. Pyrolysis 1982, 4 , 241. (6BB) Hirayanagl, S.;Kimura, K.; Sato, M.; Harada, K. Nippon Gomu Kyokalshi 1982. 55, 241. (788) Kudryavtseva, N. A.; Mikhailov, I. A.; Nikonorov, E. M.; Rakova, L. A. Khim. Tekhnol. Topi. Masel 1983, 8 , 33. (EBB) Lehrle, R. S.;Peakman, R. E.; Robb, J. C. Eur. Polym. J. 1982, 18, 517. (9BB) Llebman, S. A.; Wltterson, C.; Bowe, W. A.; Levy, E. J. Prepr. Pap.Am. Chem. Sac., Div. FuelChem. 1981, 2 6 , 1. (lOBB) Lyle, S . J.; Tehranl, M. S . J . Chromatogr. 1982, 240, 209. (1lBB) Mertens, J. J. R.; Jacobs, E.; Callaerts, A.; Buekens, A. Makromol. Chem ., Rapld Commun. 1982, 3 , 349. (1288) Novrocik, J.; Novrocikova, M.; Capek, A. Collect. Czech. Chem. Commun. 1982, 47, 476. (13138) Pacakova, V.; Nogatz, M.; Novak, V. Collect. Czech. Chem. Commun. 1982, 4 7 , 509. (1488) Riska, G. D.; Estes, S. A.; Beyer, J. 0.; Uden, P. C. Spectrochlm. Acta, Part B 1983, 388, 407. (1588) Schraftt, R. Kautsch. Gummi, Kunstst. 1983, 36, 851. (16BB) Suillvan, J. F.; Grob, R. L. J. Chromatogr. 1983, 268, 219. (1788) Tsuge, S.;Sugimura, Y.; Kobayashl, T.; Nagaya, T.; Ohtani, H. Adv. Chem. Ser. 1983, 203, 625.
Purge and Trap (ICC) Adiard, E. R.; Davenport, J. N. Chromatographia 1983, 17, 421. (2CC) Clark, A. I.; McIntyre. A. E.; Lester, J. N.; Perry, R. J. Chromatogr. 1982, 252, 147. (3CC) Drelsch, F. A.; Munson, T. 0. J. Chromatogr. Sci. 1983, 2 1 , 111. (4CC) Jackson, J. A. A.; Blair, W. R.; Brinckman, F. E.; Iverson, W. P. Environ. S d . Technol. 1982, 16, 110. (5CC) Kawata, K.; Uemura, T.; Klfune, 1.; Tominaga, Y.; Oikawa, K. Bunseki Kagaku 1982, 3 1 , 453. (6CC) Lln, S. N.; Fu, F. W. Y.; Bruckner, J. V.; Feldman, S. J . Chromatogr. . 1982, 244, 311. (7CC) Moncur, J. G.; Sharp, T. E.; Byrd, E. R. J . High Resolut. Chromatogr. Chromatogr. Commun. 1981, 4 , 603. (8CC) Pankow, J. F.; Isabelle, L. M.; Kristensen, T. J. Anal. Chem. 1982, 5 4 ,. 1815. - -
(9CC) Schaefer, J. Flavour 81, Weurman Symp. 3rd 1981, 301. (1OCC) Tangerman, A.; Meuwese-Arends, M. T.; Van Tongeren, J. H. M. Clln. Chlm. Acta 1983, 130, 103. (11CC) Turner, A. J. Ger. Offen. DE 3 139479, 13 May 1982, GB Appl. 80/32,745, 10 Oct. 1980. Headspace Gas Chromatography (IDD) Barnett, D.; Davls, E. G. J . Chromatogr. Scl. 1983, 21, 205. (2DD) Chialva, F.; Gabri, G.; Llddle, P. A. P.; Ulian, F. J. High Resolut. Chromatogr. Chromatogr. Commun. 1982, 5 , 182. (3DD) Davis, E. G.; Barnett, D..; Moy, P. M. J. Food Technol. 1983, 18, 233. (4DD) Dong, M. W. Chromatographia 1981, 14, 447. (5DD) Entz, R. C.; Hoilifleld, H. C. J. Agrlc. Food Chem. 1982, 30, 84. (6DD) Entz, R. C.; Thomas, K. W.; Diachenko, G. W. J. Agric. Food Chem. 1982, 3 0 , 846. (7DD) Etare, L. S.;Kolb, B.; Hurt, S. G. Am. Lab. 1983, 15, 76. (8DD) Gagllardl, P.; Verga, G. R. Chem. Foods Beverages: Recent Dev. 1982, 49. (9DD) House, M. Anal. Proc. 1983, 2 0 , 423. (IODD) Kettrup, A. TrAC, Trends Anal. Chem. 1982, 1, 142.
Anal. Chem. 1984, 56, 199R-212R (11DD) Kettrup, A,; Stenner, H.; Weber, H. Ber.-Dtsch. Ges. Mlneraloelwlss Kohlechem. 1982, 268. (12DD) Kolb, B. LaborPraxls 1982,6, 156. (l3DD) Kolb, B. Chromatographla 1982, 15, 587. (14DD) Larsson, L. Anal. Chem. Symp. Ser. 1983, 13, 193. (15DD) Leggett, D. C. Report 1981, CRREL-SR-81-26; Order No. ADA108345. NTIS from Gov. Rep. Announce. Index 1982, 8 2 , 1540. (16DD) Llebl. M.; Seeleltner, G. Mlit. Versuchssfn Qaerungsgewerbe Wien 1982, 36. 81. (17DD) Ott, U.; Llardon, R. Flavour 81 Weurman Symp. 3rd 1981, 323. (18DD) Pausch, J. B.; McKalen, C. A. Rubber Chem. Technol. 1983, 5 6 ,
.
.
__
AAO.
(19DD)- Safersteln, R.; Park, S. A. J. Forensic Scl. 1982,2 7 , 484. (20DD) Sakane, Y.; Nltanda, T.; Shlmoda, M.; Osajlma, Y. Nlppon Shokuhln Kogyo Gakkalshi 1983,3 0 , 108. (2100) Shaw, D. A.; Anderson, T. F. Ind. Eng. Chem. Fundam. 1983,22, 79. (22DD) Termonla, M.; De Meyer, A.; Wybauw, M.; Jacobs, H. J. High Reso/ut.Chromafogr. Chromafogr. Commun. 1982, 5, 377. (23DD) Varner, S. L.; Breder, C. V.; Fazio, T. J. Assoc. Off. Anal. Chem. 1983, 6 6 , 1067. (23DD) Vlerke, W.; Gellert, J.; Teschke, R. Arch. Toxicol. 1982, 5 1 , 91. Sampllng (IEE) DI Pasquale, 0.; Vallatl, A.; Capaccloli, T.; Galli, M. J. Chromafogr. 1982,243, 357. (2EE) Duenges, W.; Bode, J.; Hoffman, H.; Mueller, M.; Soitau, B. Proc. Int. Symp. Caplllary Chromafogr., 4th 1981, 765. (3EE) Gauthler, M.; Pllon, R.; Kutschke, K. 0. J. Chromatogr. Scl. 1982,2 0 , 283. (4EE) Greter, J.; Staahle, 0. Anal. Chem. 1982,54, 1646. (SEE) Grob, K. Jr., Comm. Eur. Communltles, 1982, Anal. Org. Mlcropolluf. Water, 57. (6EE) Grob, K., Jr.; Mueller, R. J. Chromafogr. 1982, 244, 185. (7EE) Hlltunen, R.; Laakso, I.; Hovinen, S.; Derome, J. J. Chromafogr. 1982, 237, 41. (BEE) Hlnshaw, J. V. Jr.; Felnstein, P. L. Am. Lab. 1983,Sept., 116. (9EE) Hlnshaw, J. V., Jr.; Yang, F. J. J. Hlgh Resolut. Chromatogr. Chromafogr. Commun. 1983. 6 , 554. (IOEE) Hosklka, Y. Anal. Chem. 1982,5 4 , 2433. (1 IEE) Jacobsson, S.; Berg, S.J. High Resoluf. Chromafogr. Chromafogr Commun. 1982,5, 236. (I2EE) Kovarich, E.; Munarl, F. J. High Resoluf. Chromafogr. Chromafogr. Commun. 1982,5 , 175. (13EE) Pankow, J. F.; Asher, W. E.; Isabelle, L. M. Anal. Chem. 1983, 5 5 , 1451. (14EE) Proske, M. G.; Bender, M.; Schomburg, G.; Hueblnger. E. J. Chromafogr. 1982,240, 95. (15EE) Schomburg, G. Proc. Int. Symp. Capillary Chromafogr., 4th 1981, 371.
(16EE)- Schomburg, G.; Husmann, H.; Schulz, F. J. High Resolut. Chromafogr. Chromatogr. Commun. 1982,5 , 565.
(17EE) Spencer, H. J. J. Chromatogr. 1983, 260, 164. WEE) Yang, F. J. J. High Resoluf. Chromafogr. Chromafogr. Commun. 1983, 6 , 448. Multldlmenslonal (IFF) Bellabes, R.; Granger, R.; Vergnaud, J. M. Sep. Scl. Technol. 1982, 17, 1177. (2FF) Broeteli. H.; Rletz, 0.; Sandqvist, S.; Berg, M.; Ehrsson, H. J. High Chromatogr. Chromatogr. Commun. 1982,5 , 596. (3FF) Herkner, K.; Swoboda, W. Roc. Int. Symp. Capillary Chromatogr ., 4th 1981,429. (4FF) Huber, J. F. K.; Kenndler, E.; Nyiry, W.; Oreans, M. J. Chromafogr. 1982, 247, 211. (5FF) Mueller, F. Am. Lab. 1983, i 5 , 94. (6FF) Phillips, R. J.; Knauss, K. A,; Freeman, R. R. J. High Resoluf. Chromafogr. Chromatogr. Commun. 1982, 5, 546. (7FF) Welton, B.; Goedert, M.; Lyons, T. Chromafogr. News/. 1981,9 , 56. Hlgh-Speed GC (IGG) Berezkln, V. G.; Mallk, A.; Gavrichev, V. S. J. High Resoluf. Chromatogr. Chromatogr. Commun. 1983, 6, 388. (2GG) Duarte, P. E.; McCoy, B. J. Sepf. Sei. Technol. 1982, 17, 879. (3GG) Jonker, R. J.; Poppe, H.; Huber, J. F. K. Anal. Chem. 1982, 5 4 , 2447. (4GG) Leclercq, P. A.; Scherpenzeel, G. J.; Vermeer, E. A. A.; Cramers, C. A. J. Chromafogr. 1982, 241, 61. (5GG) Schutjes, C. P. M.; Vermeer, E. A.; Rijks, J. A.; Cramers, C. A. J . Chromatogr. 1982,253, 1. (6GG) Schutjes, C. P. M. Ph.D. Dissertation, Eindhoven University of Technology, 1983. Vapor-Phase and Supercrttlcal-Fluld Chromatography Board, R.; McManiglll, D.; Weaver, H.; Gere, D. CHEMSA 1983. Fleldsted, J. C.; Rlchter, B. E., Jackson, W. P.; Lee, M. L. J. Chromafogr..l983, 279, 423. (3") Fjeldsted, J. C.; Kong, R. C.; Lee, M. L. J. Chromafogr. 1983,279, A.A.-. P (4") Futrell, J. H.; Wahrhaftig, A. L.; Randall, L. G. Report 1982, EPA6OOf3-82-061; Order No. PB82-249178. (5") Parcher, J. F. J. Chromatogr. Sci. 1983,2 1 , 346. (6") Peaden, P. A.; Fjeldsted, J. C.; Lee, M. L., Springston, S. R..; Novotny, M. Anal. Chem. 1982,54, 1090. (7") Randall, L. G., Bowman, L. M., Jr., Eds. Sep. Sci. Technol. 1981, 17, No. 1. (8") Randall, L. G. Chem. Eng. Supercrn. Fluid Cond. 1983,477. (9") Shafer, K. H.; Griffiths, P. R. Anal. Chem. 1983, 5 5 , 1939. (10") Smith, R. D.; Fjeldsted, J. C.; Lee, M. L. J. Chromatogr. 1982, 247, (1") (2")
231.
(11iiH)- Smlth, R. D.; Felix, W. D.; Fjeldsted, J. C.; Lee, M. L. Anal. Chem. 1982, 5 4 , 1883. (12") Wllsch, A.; Felst, R.; Schnelder, G. M. FluidPhase Equlllb. 1983, IO, 299.
Mossbauer Spectroscopy John G . Stevens* Department of Chemistry, University of North Carolina at Asheville, Asheville, North Carolina 28814-8467
Lawrence H. Bowen Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204
Mbssbauer spectroscopy has just completed its 25th year.
For this Analytical chemistry biannual review, it is the 10th in the series (20th year). Many of us have watched with great
interest the development of this field of research. There are now nearly 20000 articles written by research groups from over 70 different countries. Approximately 1200 articles have been published during each of the last 10 years. To commemorate the 25th anniversary of the Mossbauer effect, Editors (Deutch, Kaufmann, and de Waard) published a special issue of Hyperfine Interactions (76). After the Foreword written by R. L. Mossbauer, the volume contains the following chapters:
"Mossbauer Spectroscopyin Physical Metallurgy" (U. Gonser), "Mossbauer Spectroscopy in Magnetism" (J. Chappert), "The Impact of Mossbauer Spectroscopy on Chemistry" (T. C. Gibb), "The Understanding of Nuclear Structure Through Mossbauer Experiments" (L. Grodzins), "Mossbauer Spectroscopy of Implanted Sources" (L. Niesen "Mossbauer Studies of Valence of Fluctuations (I. Nowik), "'&n Mossbauer Spectroscopy" (T. Katila and K. Riski), "Mossbauer Spectroscopy with 191Jg31r"(F. E. Wagner), "Mossbauer Spectroscopy with Actinide Elements" (W. Potzel, J. Moser and G. M. Kalvius), "Experimental Techniques for Conversion
OO03-2700/84/0356-l99R$06.50/ 0 0 1984 American Chemical Society
109 R
